KR20190143482A - Organic electroluminescent element and process for production thereof, organic el display device, organic el lighting device, and device for production of organic electroluminescent element - Google Patents

Abstract

In the present invention, in forming the organic layer of the organic electroluminescent device by the wet film forming method, deterioration during film formation is prevented without requiring special environmental control such as nitrogen replacement using a device such as a glove box. It is an object of the present invention to provide an organic electroluminescent device having a high efficiency and a long driving life at low manufacturing cost. This invention formed into an organic layer between the anode and cathode of an organic electroluminescent element using the composition containing an organic electroluminescent element material and a solvent by the wet-film-forming method in any of the following film forming environments 1-3. It relates to a method for producing an organic electroluminescent device comprising a step of drying after.
Film-forming environment 1: Carbon dioxide concentration of 0.7 g / m 3 or less and oxygen concentration of 18 to 22% by volume
Film-forming environment 2: Sulfur oxide concentration of 2.2 µg / m 3 or less and oxygen concentration of 18 to 22% by volume
Film formation environment 3: Nitrogen oxide concentration 3.1 microgram / m <3> or less, and oxygen concentration 18-22 volume%

Description

ORGANIC ELECTROLUMINESCENT ELEMENT AND PROCESS FOR PRODUCTION THEREOF, ORGANIC EL DISPLAY DEVICE, ORGANIC EL LIGHTING DEVICE, AND DEVICE FOR PRODUCTION OF ORGANIC ELECTROLUMINESCENT ELEMENT}

TECHNICAL FIELD This invention relates to the manufacturing method of an organic electroluminescent element, an organic electroluminescent element, an organic electroluminescence display, organic electroluminescent illumination, and the manufacturing apparatus of an organic electroluminescent element.

Laminated organic electroluminescence using an evaporation method by Kodak Corp. (electro luminescence: sometimes abbreviated as "EL" is sometimes abbreviated)) Since the release of the device, the development of an organic EL display and an organic EL illumination is actively performed. Organic EL displays and organic EL lighting are being put into practical use at present.

In such a stacked organic electroluminescent device, a plurality of organic layers (for example, a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, etc.) are laminated between an anode and a cathode. Vacuum deposition is known as a method of forming these organic layers. However, in the vacuum deposition method, it is sometimes difficult to obtain a homogeneous and defect-free thin film, and furthermore, since a long time is required to form a plurality of organic layers, there is a problem in terms of manufacturing efficiency of the device.

On the other hand, the technique which forms the some organic layer of a laminated organic electroluminescent element by the wet-film-forming method is reported. For example, in patent document 1, the organic electroluminescent element which has an organic thin film formed using the organic thin film formation solution which melt | dissolved the low molecular organic material in the solvent is described.

On the other hand, when forming the organic layer in an organic electroluminescent element by the above-mentioned wet film-forming method, it is generally known that the characteristic of the organic electroluminescent element obtained will deteriorate when film-forming is performed in air | atmosphere.

On the other hand, the technique regarding manufacture of the organic electroluminescent element for avoiding deterioration by air | atmosphere is disclosed. For example, Patent Documents 2 and 3 describe a method for producing an organic EL device in an inert gas in which water and oxygen are suppressed to a predetermined concentration or less.

Japanese Laid-Open Patent Publication 2004-199935 Japanese Laid-Open Patent Publication 2003-217840 Japanese Laid-Open Patent Publication 2006-261055

However, in order to make the method of patent documents 2 and 3 cut off oxygen and water, it is necessary to perform nitrogen substitution using apparatuses, such as a glove box, and manufacturing cost becomes easy. Moreover, especially when using a large substrate and using continuous processes, such as a roll-to-roll, it was difficult to improve productivity.

In view of the above problems, the present invention does not require special environmental control such as performing nitrogen substitution using a glove box or the like in forming an organic layer of an organic electroluminescent device by a wet film formation method. It is an object of the present invention to provide an organic electroluminescent device which can prevent deterioration during film formation and has a high efficiency and a long driving life at low cost.

The present invention particularly provides a method of manufacturing an organic electroluminescent device for producing an organic electroluminescent device having a high efficiency and a long driving life, with a high production efficiency, in a method for producing an organic electroluminescent device for forming a light emitting layer by a wet film formation method. It is a task to do it.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. Here, conventionally, when the organic layer is formed by the wet film formation method, it is necessary to carry out in an environment in which oxygen or moisture is removed, and for this purpose, a special device such as a glove box is required, resulting in an increase in manufacturing cost. At the same time, it was considered a difficult factor to improve production efficiency.

Therefore, it was speculated that the above problems can be solved by first performing an environment in which the organic layer is formed by the wet film formation method in the air without using a special device such as a glove box.

However, as described in Patent Documents 2 and 3, oxygen and moisture in the film forming environment affect the device characteristics, and it is common knowledge of those skilled in the art to block them.

Here, as a result of intensive studies, the present inventors have found that other specific components have a greater influence on the driving life and efficiency of the device than the effects of components such as oxygen and moisture in the film forming environment, and thus the present invention is reached. It was.

That is, the summary of this invention is a manufacturing method of the following organic electroluminescent element, organic electroluminescent element, organic electroluminescence display, organic electroluminescent illumination, and manufacturing apparatus of organic electroluminescent element.

[1] A method for producing an organic electroluminescent device having an organic layer between an anode and a cathode,

The step of forming at least one layer included in the organic layer is a film forming step of forming a film by a wet film forming method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent, and drying the film formed. Including a drying process,

The film-forming process is performed in the environment whose carbon dioxide concentration is 0.7 g / m <3> or less and oxygen concentration is 18-22 volume%.

[2] A method for producing an organic electroluminescent device having an organic layer between an anode and a cathode,

The step of forming at least one layer included in the organic layer is a film forming step of forming a film by a wet film forming method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent, and drying the film formed. Including a drying process,

The film-forming process is performed in the environment whose sulfur oxide concentration is 2.2 microgram / m <3> or less, and the oxygen concentration is 18-22 volume%.

[3] A method for producing an organic electroluminescent device having an organic layer between an anode and a cathode,

The step of forming at least one layer included in the organic layer is a film forming step of forming a film by a wet film forming method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent, and drying the film formed. Including a drying process,

The manufacturing method of the organic electroluminescent element which performs this film-forming process in the environment whose nitrogen oxide concentration is 3.1 microgram / m <3> or less, and oxygen concentration is 18-22 volume%.

[4] A method for producing an organic electroluminescent device having an organic layer between an anode and a cathode,

The step of forming at least one layer included in the organic layer is a film forming step of forming a film by a wet film forming method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent, and drying the film formed. Including a drying process,

The film-forming process is performed in the environment whose oxygen concentration is 18-22 volume%, and in the environment which satisfy | fills at least 2 of following (1)-(3), The manufacturing method of the organic electroluminescent element.

(1) Carbon dioxide concentration is 0.7 g / m 3 or less

(2) sulfur oxide concentration is 2.2 μg / m 3 or less

(3) Nitrogen oxide concentration is 3.1 μg / m 3 or less

[5] A method for producing an organic electroluminescent device having an organic layer between an anode and a cathode,

The step of forming at least one layer included in the organic layer is a film forming step of forming a film by a wet film forming method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent, and drying the film formed. As a method comprising a drying step,

The film forming step is performed under an environment where the oxygen concentration is 18 to 22% by volume and the absolute humidity is 15 g / kg (DA) or less, and under an environment that satisfies at least one of the following (1) to (3), Method for producing an organic electroluminescent device.

(1) Carbon dioxide concentration is 0.7 g / m 3 or less

(2) sulfur oxide concentration is 2.2 μg / m 3 or less

(3) Nitrogen oxide concentration is 3.1 μg / m 3 or less

[6] The method for producing an organic electroluminescent device according to any one of [1] to [5], wherein the layer obtained through the film forming step and the drying step is a light emitting layer.

[7] The method for producing an organic electroluminescent element according to any one of [1] to [6], wherein the layer obtained through the film forming step and the drying step is a hole transport layer.

[8] The organic material according to any one of the above [1] to [7], in which the organic electroluminescent device material contains at least one selected from the group consisting of an organometallic complex, an aromatic amine compound, and an anthracene derivative. Method of manufacturing an electroluminescent device.

[9] An organic electroluminescent element produced by the method for producing an organic electroluminescent element according to any one of [1] to [8].

[10] An organic EL display device having the organic electroluminescent element according to the above [9].

[11] An organic EL illumination having the organic electroluminescent element according to the above [9].

[12] An apparatus for manufacturing an organic electroluminescent element having an organic layer between an anode and a cathode,

Film forming means for forming at least one layer in the organic layer by a wet film forming method using an organic electroluminescent element composition containing an organic electroluminescent element material and a solvent, drying means for drying the formed film;

The manufacturing apparatus of the organic electroluminescent element which has air purification means which reduces any one or more of carbon dioxide concentration, sulfur oxide concentration, and nitrogen oxide concentration in the atmosphere of the film-forming means.

According to the present invention, in forming the organic layer of the organic electroluminescent device by the wet film forming method, even if the film forming step is performed in an environment containing oxygen or moisture, the device with less deterioration in light emission life can be provided. That is, according to the present invention, it is possible to manufacture an organic electroluminescent element having a high efficiency and a long driving life at low cost without requiring a special device such as a glove box.

1: is sectional drawing which shows an example of the structure of the organic electroluminescent element of this invention typically.
FIG. 2 is a diagram schematically showing an example of an internal structure of an apparatus for manufacturing an organic electroluminescent element of the present invention. FIG.

EMBODIMENT OF THE INVENTION Although embodiment of this invention is described in detail below, description of the element | module described below is an example (representative example) of embodiment of this invention. The present invention is not specified in these contents unless it deviates from the summary.

[1] method of manufacturing organic electroluminescent device

The manufacturing method of the organic electroluminescent element of this invention uses the composition for organic electroluminescent elements containing an organic electroluminescent element material and a solvent, the film-forming process to form a film by the wet-film-forming method, and the drying process which dries the film formed into a film. In forming the organic layer of an organic electroluminescent element via, it is characterized by performing wet film-forming in any of the following film forming environments 1-3.

Film-forming Environment 1: Environment with Carbon Dioxide Concentration of 0.7g / m 3 or Less and Oxygen Concentration of 18 to 22% by Volume

Film-forming Environment 2: Environment with Sulfur Oxide Concentration of 2.2 µg / m 3 or Less and Oxygen Concentration of 18 to 22 Volume%

Film formation environment 3: Environment where nitrogen oxide concentration is 3.1 microgram / m <3> or less, and oxygen concentration is 18-22 volume%.

[Organic layer for film formation]

In the manufacturing method of the organic electroluminescent element of this invention, what is necessary is just an organic layer formed between the anode and cathode of an organic electroluminescent element as a organic layer formed by wet-forming in the environment of the said film-forming environments 1-3. Although not preferred, it is a light emitting layer and / or a hole transporting layer.

[Film formation environment]

EMBODIMENT OF THE INVENTION Below, the film-forming environment which concerns on this invention is demonstrated.

에 About oxygen｝

In the film forming environment according to the present invention, when the carbon dioxide concentration, sulfur oxide concentration or nitrogen oxide concentration is controlled, the oxygen concentration can be made equal to the oxygen concentration contained in the atmosphere. Therefore, in film-forming environments 1-3, oxygen concentration is the range of 18-22 volume% similarly to normal air | atmosphere.

That is, in the present invention, by controlling only the carbon dioxide concentration, sulfur oxide concentration, or nitrogen oxide concentration in the atmosphere, a device having high efficiency and long life can be obtained by wet film formation in the air without requiring a special device such as a glove box. have.

탄소 About carbon dioxide｝

(1) measuring method

The carbon dioxide concentration in the environment can be measured, for example, by gas chromatography (GC / TCD method) equipped with a thermal conductivity detector. Specifically, it measures in the following order. A gas chromatograph is measured by introducing a gas in which a He standard gas containing a carbon dioxide at a predetermined concentration and nitrogen gas are mixed at various flow rate ratios into a GC / TCD apparatus. A calibration curve for carbon dioxide and GC / TCD signal strength is prepared. Next, a predetermined amount, for example, 0.5 cm 3 of gas to be measured is collected in a syringe having a cock at the tip, and this is introduced into the above-described apparatus to perform GC / TCD measurement. The carbon dioxide concentration is quantified by calculating the amount of carbon dioxide in 0.5 cm 3 from the calibration curve described above. As a GC / TCD apparatus, Shimadzu Corporation make "GC-2010" etc. can be used, for example. In addition, the carbon dioxide concentration in the Example mentioned later is also measured by this method. The detection limit of the carbon dioxide concentration in this method is 0.04 g / m 3. In addition, if the measurement similar to the said apparatus is possible, the GC / TCD measurement may use the apparatus other than that.

(2) Reasons for Controlling Carbon Dioxide Concentration

Carbon dioxide is normally contained in about 0.5-1.0 g / m <3> in air | atmosphere. In this invention, the carbon dioxide concentration in a film-forming environment is made into a predetermined value or less for the following reasons.

It is known that carbon dioxide reacts with moisture in the atmosphere to become carbonate ions. It is thought that this carbonate ion mixes in the organic layer of an organic electroluminescent element, and produces the quench of the electric charge which moves in an organic layer. The change in carrier balance in the organic layer due to this quench is considered to be a factor of lowering efficiency and shortening the life of the organic EL device.

Therefore, in order to avoid generation | occurrence | production of the said quencher, it is thought that it is necessary to reduce carbon dioxide in a film-forming environment.

(3) carbon dioxide concentration

In the film-forming environment 1, it is preferable that the carbon dioxide concentration in the film-forming environment is low in that the fall of the organic electroluminescent element characteristic by the inhibition of the charge transfer in an organic layer does not occur easily. Specifically, the carbon dioxide concentration in the film forming environment is a value measured by the above measuring method, and is usually 0.7 g / m 3 or less, preferably 0.5 g / m 3 or less. Moreover, since the lower the carbon dioxide concentration in a film-forming environment, it is so preferable that it is low, there is no minimum in particular, but it is 0.00004 g / m <3> normally.

About sulfur oxides

(1) measuring method

Sulfur oxides in the environment are derived from combustion of fossil fuels, volcanic gases, and the like, and the sulfur oxide concentration can be measured by ion chromatography, for example. In addition, sulfur oxide is a general term of oxides of sulfur, such as sulfur monoxide, sulfur dioxide, and sulfur trioxide. Specifically, the sulfur oxide concentration can be quantified by collecting the gas to be measured in water at 1.5 L / min for 1 hour, and analyzing this by using an ion chromatograph analyzer "DX500 type" (manufactured by DIONEX). . In addition, the sulfur oxide concentration in the Example mentioned later is also measured by this method. The detection limit of sulfur oxide concentration in this method is 0.1 µg / m 3. In addition, if the measurement similar to the said apparatus is possible, the measurement of a sulfur oxide concentration may be performed using another apparatus.

(2) Reasons to Control Sulfur Oxide Concentration

Sulfur oxides are usually contained in the atmosphere at about 50 to 1700 µg / m 3. In this invention, sulfur oxide concentration in an environment is made into a predetermined value or less for the following reasons.

Sulfur oxides are known to react with moisture in the atmosphere to form sulfuric acid, which is a powerful oxidant. In addition, sulfur dioxide and sulfur trioxide, which are one type of sulfur oxide, function as reducing agents and oxidizing agents, respectively. Therefore, it is thought that the action of the oxidizing agent or the reducing agent causes the organic compound constituting the organic electroluminescent element to be oxidized or reduced, thereby changing the properties of the organic compound, for example, ionization potential, electron affinity, carrier mobility, and the like. do. For this reason, it is thought that the lifetime of an organic electroluminescent element becomes short and efficiency falls.

In addition, it is thought that an acid such as sulfuric acid is mixed into the organic layer of the organic electroluminescent element, thereby producing a quench of charges that move in the organic layer. It is thought that the change of the carrier balance in this organic layer becomes a factor of reducing efficiency and shortening of an organic electroluminescent element.

Therefore, in order to avoid formation of the quencher due to the above-mentioned deterioration of organic compounds and incorporation of an acid, it is considered necessary to reduce sulfur oxides in the environment.

(3) sulfur oxide concentration

In the film-forming environment 2, it is preferable that the sulfur oxide concentration in the film-forming environment is low in that the fall of the organic electroluminescent element characteristic by a change of an organic layer or the inhibition of the charge transfer in an organic layer hardly occurs. Specifically, the sulfur oxide concentration in the film forming environment is a value measured by the above measuring method, and is usually 2.2 µg / m 3 or less, preferably 1.2 µg / m 3 or less. Moreover, since the lower the sulfur oxide concentration in a film forming environment, the more preferable it is, although there is no minimum in particular, it is 0.0001 microgram / m <3> normally.

에 About Nitrogen Oxides｝

(1) measuring method

Nitrogen oxides in the environment are derived from the combustion of fossil fuels. In addition, nitrogen oxides are nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), nitrous oxide (dinitrogen monoxide) (N ₂ O), dinitrogen trioxide (N ₂ O ₃ ), dinitrogen tetraoxide (N ₂ O ₄ ), dinitrogen pentoxide. General term for oxides of nitrogen such as nitrogen (N ₂ O ₅ ). Nitrogen oxide concentration can be measured by ion chromatography, for example. Specifically, the quantitative determination of the nitrogen oxide concentration in the gas is measured by collecting the measurement target gas in water at 1.5 L / min for 1 hour, and analyzing this using an ion chromatograph analyzer "DX500 type" (manufactured by DIONEX). can do. In addition, the nitrogen oxide concentration in the Example mentioned later is also measured by this method. The detection limit of nitrogen oxide concentration in this method is 0.1 µg / m 3.

In addition, if the measurement similar to the said apparatus is possible, the measurement of nitrogen oxide concentration may be performed using another apparatus.

(2) Reasons to control nitrogen oxides

Nitrogen oxide is normally contained in about 70-5400 microgram / m <3> in air | atmosphere. In the present invention, the nitrogen oxide concentration in the environment is set to a predetermined value or less for the following reasons.

Nitrogen oxides are known to react with moisture in the atmosphere to become nitric acid, a powerful oxidant. By the action of this oxidizing agent, it is thought that the organic compound constituting the organic light emitting element is oxidized, and the original properties of the organic compound, for example, ionization potential, electron affinity, carrier mobility, and the like are changed. For this reason, it is thought that the lifetime of an organic electroluminescent element becomes short and efficiency falls.

Moreover, it is thought that nitrogen dioxide which is a radical molecule which has a non-dielectron as one type of nitrogen oxide mixes in the organic layer of an organic electroluminescent element, and produces the quench of the electric charge which moves in an organic layer. And it is thought that the change of the carrier balance in the organic layer by this becomes a factor of reducing the efficiency and short lifetime of an organic electroluminescent element.

Therefore, in order to avoid formation of the quencher due to the above-mentioned deterioration of organic compounds and incorporation of an acid, it is considered necessary to reduce nitrogen oxides in the environment.

(3) nitrogen oxide concentration

In the film-forming environment 3, it is preferable that the nitrogen oxide concentration in the film-forming environment is low because it is hard to produce the fall of the organic electroluminescent element characteristic by the deterioration of an organic layer or the inhibition of the charge transfer in an organic layer. Specifically, the nitrogen oxide concentration in the film forming environment is a value obtained by the above measuring method, and is usually 3.1 µg / m 3 or less, preferably 2.5 µg / m 3 or less. Moreover, since the lower the nitrogen oxide concentration in a film-forming environment, the lower the preferable, there is no particular lower limit, but it is usually 0.0001 µg / m 3.

Moreover, the wet film-forming environment which concerns on this invention should just satisfy | fill at least 1 of the said film-forming environments 1-3. Moreover, it is preferable that the wet film-forming environment which concerns on this invention satisfy | fills at least any two of the said film-forming environments 1-3, and it is especially preferable to satisfy all three of the said film-forming environments 1-3.

｝ Measurement method of film formation environment｝

The wet film-forming environment according to the present invention is prepared by reducing the carbon dioxide concentration, sulfur oxide concentration and / or nitrogen oxide concentration in the environment, for example, by removing carbon dioxide, sulfur oxide and / or nitrogen oxide from the atmosphere. Can be. Moreover, it can also prepare by mixing inert gas, such as nitrogen and argon, and oxygen.

｝ Means for reducing carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration｝

As a method of reducing the carbon dioxide concentration, sulfur oxide concentration, and nitrogen oxide concentration in an environment, the method of using a chemical filter, activated carbon, or water is mentioned, for example. These may be used individually by 1 type and may use 2 or more types by arbitrary combinations and a sequence.

Below, the definition of each means, a specific example, a reason for compatibility, etc. are shown.

(1) chemical filter

The chemical filter in this invention has a function which removes specific components, such as dust and an inorganic gas component, from gas. In a chemical filter, the thing which has the adsorption function, such as activated carbon, activated alumina, and the like which the component which can remove a specific gas component is welded is used normally.

The chemical filter is not particularly limited as long as the effects of the present invention are not impaired. As a chemical filter, a chemical guard (made by Nichias Corporation), a pure light filter (made by Nippon Puretec Co., Ltd.), a pure melt (made by Nippon Inorganic Corporation), TIOS (made by Takasago Thermochemistry Co., Ltd.), etc. are mentioned, for example.

Chemical filters typically have high adsorption and collection performance of breathable and gaseous impurity components, are inexpensive, and are easily available. Therefore, in these aspects, it is preferable to use a chemical filter in order to set it as film-forming environments 1-3.

(2) activated carbon

Activated carbon in the present invention is carbon having a large number of micropores. Activated carbon in the present invention usually has a large number of micropores of 1 to 20 nm which have been subjected to chemical or physical treatment in order to increase the adsorption capacity for the purpose of separating, removing, or purifying any specific substance. 90% or more of the constituent material of the activated carbon in this invention is carbon normally.

As activated carbon, there is no restriction | limiting in particular unless the effect of this invention is impaired, For example, Shirasagi (made by Nippon Enviro Chemicals), Kura Cole (manufactured by Kureray Chemical Co., Ltd.), and carbon (Mitsubishi Chemical) Cargon company), activated carbon (made by Futura Chemical Co., Ltd.), etc. are mentioned. Since activated carbon is usually physically adsorbed, the adsorption rate is high, it is difficult to depend on the flow rate of the introduced air, and the activated carbon used again can be reused, the cost is low, and it is easy to obtain. Therefore, in these aspects, it is preferable to use activated carbon in order to make film forming environments 1-3.

(3) water

The water used for reducing the carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration in the environment is not particularly limited. Carbon dioxide, sulfur oxides, nitrogen oxides, and the like are easily removed, and demineralized water, water passed through an ion exchange resin, pure water, ultrapure water, and the like are preferable.

In the case of using water, a desired effect can be obtained, for example, by a method of passing air in water, a method of spraying water on the air in the flow, and a countercurrent contact between the air and water.

Especially in this invention, it is preferable to use a chemical filter among the above.

In the present invention, the carbon dioxide concentration in the air, sulfur, and the like are caused by venting air supplied to the film forming environment to the air purifying means consisting of the chemical filter, the activated carbon packed layer, the aqueous layer, or a combination thereof. After reducing any one or more of an oxide concentration and a nitrogen oxide concentration, it can be supplied to the film-forming environment of an organic layer, and the above-mentioned film-forming environments 1-3 can be implement | achieved.

In this case, the supply speed (air volume) of the air to the air purification means is not particularly limited as long as the effects of the present invention are not impaired, but is usually 0.1 m / s or more and 1.0 m / s or less. If it is in this range, since the target object in air is easy to fully remove by the said air purification means, it is preferable.

에 About other environmental items｝

As mentioned above, the wet film-forming environment in this invention should just control carbon dioxide concentration, sulfur oxide concentration, or nitrogen oxide concentration, and there is no restriction | limiting in particular about other environmental items. However, a small amount of moisture is preferable in that condensation hardly occurs, and on the other hand, many are preferable in that static electricity hardly occurs. Therefore, it is 15 g / kg (DA) or less as an absolute humidity, 12 g / kg (DA) or less, especially 9 g / kg (DA) or less, 2 g / kg (DA) or more and 4 g / kg ( It is preferable that it is DA) or more, especially 5 g / kg (DA) or more. Humidity can be measured using various hygrometers.

[Composition for Organic Electroluminescent Device]

Next, the composition for organic electroluminescent elements used for formation of the organic layer by the said wet film-forming method is demonstrated.

This composition for organic electroluminescent elements contains an organic electroluminescent element material and a solvent normally.

The organic electroluminescent element material used for the composition for organic electroluminescent elements is suitably selected according to the kind of organic layer formed into a film by the wet-film-forming method. The material suitable for formation of a light emitting layer and a hole transporting layer as an organic layer is demonstrated below.

광 Light Emitting Layer Material｝

As a light emitting layer material, an organometallic complex, an aromatic amine compound, an anthracene derivative, etc. are mentioned.

In the present invention, in the case where the organic electroluminescent device material is a light emitting layer material, that is, in the case where the composition for the organic electroluminescent device is a composition for a light emitting layer, the reason why a particularly large effect is obtained by the configuration of the present invention is as follows. Guess as

An organic electroluminescent element has a light emitting layer between an anode and a cathode, and emits light by the energy in the light emitting layer, especially when the light emitting layer material returns from an excited state to a ground state. That is, it means that the molecule | numerator of an excited state always exists in the light emitting layer of the organic electroluminescent element at the time of driving. Here, when sulfur oxide or nitrogen oxide exists in a light emitting layer, it is estimated that redox degradation of a light emitting layer material is carried out. If carbon dioxide, sulfur oxides, or nitrogen oxides are present in the light emitting layer, the charges are quenched, and it is estimated that it affects the driving voltage and current efficiency of the device to be obtained, in particular, the driving life. In short, in the present invention, it is preferable to satisfy at least one of the film forming environments 1 to 3 when wet film formation using the composition for the light emitting layer.

Hereinafter, the organometallic complex, aromatic amine compound, and anthracene derivative which can be used suitably as a light emitting layer material are demonstrated.

<Organic metal complex>

As the organometallic complex in the present invention, for example, a long periodic table (hereinafter, unless otherwise specified, a "periodic table" shall refer to a long periodic table). Werner complex, organometallic complex, etc. which contain the metal chosen from a group as a center metal are mentioned.

Examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Among them, more preferably iridium or platinum.

As the ligand of the complex, a ligand to which (hetero) aromatics such as (hetero) arylpyridine ligand and (hetero) arylpyrazole ligand and pyridine, pyrazole, phenanthroline and the like are connected is preferable, and a phenylpyridine ligand and phenylpyrazole Ligands are particularly preferred. Here, (hetero) aryl represents an aromatic or heteroaromatic group.

Specific examples of the organometallic complex include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum and tris (2-phenylpyridine). Osmium, tris (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, etc. are mentioned.

Especially as a phosphorescent organometallic complex in an organometallic complex, The compound preferably represented by following formula (III) or formula (IV) is mentioned.

ML _(qj) L ' _j (Ⅲ)

(In formula (III), M represents a metal, q represents the valence of the said metal. Moreover, L and L 'represent a bidentate ligand. J represents the number of 0, 1, or 2.)

[Formula 1]

(In formula (IV), M <^7> represents a metal and T represents a carbon atom or a nitrogen atom. R <^92> -R <^95> represents a substituent each independently. However, when T is a nitrogen atom, R <^94> And R ⁹⁵ is absent)

Hereinafter, the compound represented by Formula (III) is demonstrated first.

In formula (III), M represents arbitrary metals. As a preferable specific example of M, the above-mentioned metal etc. are mentioned as a metal chosen from periodic table group 7-11.

In addition, in Formula (III), the bidentate ligand L represents a ligand having the following partial structure.

[Formula 2]

In the partial structure of L, ring A1 represents the aromatic ring group which may have a substituent. Here, an aromatic ring group represents an aromatic hydrocarbon group or an aromatic heterocyclic group.

As this aromatic hydrocarbon group, the group derived from the 5- or 6-membered monocyclic ring or the 2-5 condensed ring etc. are mentioned. In addition, about the "derived group" in this invention, group obtained by removing 1 or more hydrogen atoms from the structure used as the origin of origin is shown. For example, a benzene ring "derived group" shows the group obtained by removing 1 or more hydrogen atoms of a benzene ring like a phenyl group and a phenylene group.

Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring and fluorine. The monovalent group derived from a lanten ring, a fluorene ring, etc. are mentioned.

Examples of the aromatic heterocyclic group include a single ring of 5 or 6 membered ring or a group derived from 2 to 4 condensed ring.

Specific examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolomidazole ring, Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, Pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring And monovalent groups derived from an azulene ring.

In addition, in the partial structure of L, ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.

Examples of the nitrogen-containing aromatic heterocyclic group include a monocyclic ring of 5 or 6 membered ring or a group derived from 2 to 4 condensed ring.

Specific examples include pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolomidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, Furopyrrole ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, Monovalent groups derived from a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and the like.

Examples of the substituent which the ring A1 or the ring A2 may each have include a halogen atom; alkyl group; alkenyl group; alkoxycarbonyl group; alkoxy group; aryloxy group; dialkylamino group; diarylamino group; carbazolyl group; acyl group; halo Alkyl group; Cyano group; Aromatic hydrocarbon group, etc. are mentioned.

In Formula (III), the bidentate ligand L 'represents a ligand having the following partial structure. However, in the following formula, "Ph" represents a phenyl group.

[Formula 3]

Especially, as L ', the following ligand is preferable from a viewpoint of stability of a complex.

[Formula 4]

As a compound represented by Formula (III), More preferably, the compound represented by following formula (IIIa), (IIIb), (IIIc) is mentioned.

[Formula 5]

(In formula (IIIa), M <^4> represents the same metal as M, w represents the valence of the said metal, ring A1 represents the aromatic ring group which may have a substituent, and ring A2 may have a substituent, Represents a nitrogen-containing aromatic heterocyclic group)

[Formula 6]

(Wherein (Ⅲb), M ⁵ is, represents the same metal as M, w is, represents the valence of the metal, ring A1 is and represents an aromatic ring which may have a substituent, and ring A2 is, which may have a substituent Represents a nitrogen-containing aromatic heterocyclic group)

[Formula 7]

(In formula (IIIc), M <^6> represents the same metal as M, w represents the valence of the said metal, j represents 0, 1 or 2, and ring A1 and ring A1 'are respectively independently. Represents an aromatic ring group which may have a substituent, and ring A2 and ring A2 'each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent)

In the formulas (IIIa) to (IIIc), preferred examples of ring A1 and ring A1 'include phenyl group, biphenyl group, naphthyl group, anthryl group, thienyl group, furyl group, benzothienyl group, benzofuryl group, and pyri A dill group, a quinolyl group, an isoquinolyl group, a carbazolyl group, etc. are mentioned.

In the formulas (IIIa) to (IIIc), preferred examples of the ring A2 and the ring A2 'include a pyridyl group, a pyrimidyl group, a pyrazyl group, a triazyl group, a benzothiazole group, a benzoxazole group, a benzimidazole group and a qui A teal group, an isoquinolyl group, a quinoxalyl group, a phenanthridyl group, etc. are mentioned.

As a substituent which the compound represented by said Formula (IIIa)-(IIIc) may have, a halogen atom; an alkyl group; an alkenyl group; an alkoxycarbonyl group; an alkoxy group; an aryloxy group; a dialkylamino group; a diarylamino group; carbazolyl group ACyl group, a haloalkyl group, a cyano group, etc. are mentioned.

In addition, these substituents may be linked to each other to form a ring. As a specific example, you may form one condensed ring by combining the substituent which ring A1 has and the substituent which ring A2 has, or the substituent which ring A1 'has, and the substituent which ring A2' has. As such a condensed ring, a 7,8- benzoquinoline group etc. are mentioned.

Especially, as a substituent of ring A1, ring A1 ', ring A2, and ring A2', More preferably, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a haloalkyl group, a diarylamino group, and carbazolyl group Etc. can be mentioned.

Preferred examples of the addition, formula ^{(Ⅲa) ~ M 4 ~ M} 6 in (Ⅲc) is ruthenium, rhodium, palladium, silver, it may be mentioned rhenium, osmium, iridium, platinum or gold.

The specific example of the organometallic complex represented by said Formula (III) and (IIIa)-(IIIc) is shown below. However, the organometallic complex represented by the formulas (III) and (IIIa) to (IIIc) is not limited to the following compounds.

[Formula 8]

[Formula 9]

Among the organometallic complexes represented by the above formula (III), in particular, compounds having a 2-arylpyridine-based ligand as the ligand L and / or L 'are preferable. That is, the compound which has 2-arylpyridine, what the arbitrary substituent couple | bonded with this, and what consists of condensation of arbitrary groups to this is preferable.

Moreover, the compound of international publication 2005/019373 can also be used as a light emitting layer material.

Next, the compound represented by Formula (IV) is demonstrated.

[Formula 10]

In formula (IV), M ⁷ represents a metal. As a specific example of M <^7> , the metal chosen from group 7-11 of the periodic table mentioned above is mentioned. Among these, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold are preferable, and bivalent metals such as platinum and palladium are particularly preferable.

In formula (IV), R ⁹² and R ⁹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, an alkoxy group, An alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group, or an aromatic heterocyclic group is shown.

In addition, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent a substituent represented by the same example as R ⁹² and R ⁹³ . In addition, when T is a nitrogen atom, there are no R ⁹⁴ and R ⁹⁵ .

In addition, R ⁹² to R ⁹⁵ may further have a substituent. When R <^92> -R <^95> has a substituent, there is no restriction | limiting in particular in the kind, Any group can be made into a substituent.

In addition, any two or more groups in R ⁹² to R ^{95 may} be linked to each other to form a ring.

Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by formula (IV) are shown below. However, the organometallic complex represented by Formula (IV) is not limited to the following example. In addition, in the following chemical formula, "Me" represents a methyl group and Et represents an ethyl group.

[Formula 11]

The molecular weight of these organometallic complexes is arbitrary unless the effect of this invention is impaired remarkably. The molecular weight of these organometallic complexes is 10000 or less normally, Preferably it is 5000 or less, More preferably, it is 4000 or less, More preferably, it is 3000 or less. Moreover, the molecular weight of these organometallic complexes is 100 or more normally, Preferably it is 200 or more, More preferably, it is 300 or more, More preferably, it is 400 or more. The molecular weight of the organometallic complex is preferably large in that it is excellent in heat resistance, hardly generates gas, excellent in film quality when a film is formed, and hardly changes in morphology of the organic electroluminescent device due to migration or the like. Moreover, since the molecular weight of an organometallic complex is easy to refine | purify the said organometallic complex, and is easy to melt | dissolve in a solvent, it is preferable that it is small.

In addition, any 1 type of organometallic complex mentioned above may be used and may use 2 or more types together by arbitrary combinations and a ratio.

<Aromatic amine compound>

In this invention, it is preferable that the aromatic amine compound as a light emitting layer material captures a hole efficiently in a light emitting layer, and is represented by following formula (A).

[Formula 12]

(In Formula (A), Ar <^31> is group chosen from a biphenyl group, a terphenyl group, a stilbene group, and a distyryl aromatic group, Ar <^32> and Ar <^33> are respectively independently a hydrogen atom or C6-C20 It is a phosphorus aromatic ring group, and Ar <^31> , Ar <^32> and Ar <^33> may have a substituent. A is an integer of 1-4.)

Here, an aromatic ring group represents an aromatic hydrocarbon group or an aromatic heterocyclic group. In addition, at least one of Ar ³² and Ar ³³ is preferably substituted with a styryl group.

Here, as a C6-C20 aromatic ring group, aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, anthranyl group, a phenanthryl group, and a terphenyl group, etc. are mentioned.

Moreover, as an aromatic amine compound used as a host material of a light emitting layer, since it captures a hole efficiently in a light emitting layer, it is also preferable to represent with following formula (B).

[Formula 13]

(In Formula (B), Ar ³⁴ is a substituted or unsubstituted aromatic carbon group having 10 to 40 carbon atoms. Ar ³⁵ and Ar ³⁶ are each independently a substituted or unsubstituted aromatic carbon group having 5 to 40 atoms. B is an integer of 1 to 4)

Here, as the aromatic ring group having 10 to 40 nuclear carbon atoms for Ar ³⁴ , for example, a naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, chrysenyl group, coronyl group, biphenyl group, terphenyl group, diphenylanthra And a vinyl group, carbazolyl group, benzoquinolyl group, fluoranthenyl group, acenaphthofluoranthenyl group, stilbene group, and the like.

As the aromatic ring group having 5 to 40 nuclear carbon atoms for Ar ³⁵ and Ar ³⁶ , for example, a phenyl group, naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, chrysenyl group, coronyl group, biphenyl group, ter Phenyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiophenyl group, oxadiazolyl group, diphenylanthranyl group, indolyl group, carbazolyl group, pyridyl group, benzoquinolyl group, fluoranthenyl group, acenaphthofluoro Lantenyl group, stilbene group, etc. are mentioned.

When these aromatic ring groups have a substituent, as a preferable substituent, a C1-C6 alkyl group (ethyl group, a methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, pentyl group, hexyl group) , A cyclopentyl group, a cyclohexyl group, etc.), an alkoxy group having 1 to 6 carbon atoms (ethoxy group, methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butoxy group, pentoxy group, A hexyloxy group, a cyclopentoxy group, a cyclohexyloxy group, etc.), an amino group substituted with 5 to 40 aromatic ring groups, an amino group substituted with a 5 to 40 aromatic ring group, and an aromatic ring group having 5 to 40 nuclear atoms The ester group which has, an ester group which has a C1-C6 alkyl group, a cyano group, a nitro group, a halogen atom, etc. are mentioned.

<< concrete example >>

Specific examples of the aromatic amine compound include the following compounds. However, the aromatic amine compound according to the present invention is not limited to the following.

[Formula 14]

[Formula 15]

[Formula 16]

<Anthracene derivative>

The anthracene derivative used as the light emitting layer material is preferably a compound represented by the following formula (V) in that the charge is efficiently transported.

[Formula 17]

(In Formula (V), Ar <^21> and Ar <^22> respectively independently represent the aromatic ring group which may have a substituent. Moreover, the anthracene ring in Formula (V) may have substituents other than Ar <^21> and Ar <^22>. do)

Ar ²¹ and Ar ²² each independently represent an aromatic ring group which may have a substituent.

Examples of the aromatic hydrocarbon group for Ar ²¹ and Ar ²² include a benzene ring or a benzene ring such as a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, chrysene ring, naphthacene ring and benzophenanthrene ring. And groups derived from a condensed ring in which ~ 5 are condensed.

Specific examples of the aromatic heterocyclic group of Ar ²¹ and Ar ²² include furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadia Sol ring, indole ring, carbazole ring, pyrrolomidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, perri Groups derived from a midine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. are mentioned.

Examples of the substituent which the aromatic ring group in Ar ²¹ and Ar ²² may have include an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkoxy group, a (hetero) aryloxy group, an alkylthio group, a (hetero) arylthio group, Organic groups, such as a cyano group, a dialkylamino group, an alkylarylamino group, and a diarylamino group, are mentioned. Among these, an alkyl group and an aromatic hydrocarbon group are preferable at the stability of a compound, and an aromatic hydrocarbon group is especially preferable.

As an alkyl group as a substituent which the aromatic ring group in Ar <^21> and Ar <^22> may have, it is preferable that it is C1-C20. Specifically, for example, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, cyclohexyl group, decyl group And octadecyl group. Among these, methyl group, ethyl group, iso-propyl group, sec-butyl group and tert-butyl group are preferable. Moreover, a methyl group and an ethyl group are preferable among these in terms of the availability of a raw material, inexpensiveness, etc., and iso-butyl group, sec-butyl group, and tert-butyl group are preferable because they have high solubility in a nonpolar solvent.

As an aromatic hydrocarbon group, it is preferable that it is C6-C25. The aromatic hydrocarbon group is preferably a monocyclic 6-membered ring or an aromatic hydrocarbon group derived from a 2 to 5 condensed ring. Specifically, for example, a benzene ring, naphthalene ring, atracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring The group derived from these etc. can be mentioned.

As an aromatic heterocyclic group, it is preferable that it is C3-C20. Specifically, for example, furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole Ring, pyrrolomidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothia Sol ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, perimidine ring, quinazoline ring, quina Groups derived from a zolinone ring, an azulene ring, etc. are mentioned.

As an alkoxy group, it is preferable that it is C1-C20. Specifically, a methoxy group, an ethoxy group, isopropyloxy group, a cyclohexyloxy group, an octadecyloxy group etc. are mentioned, for example.

As a (hetero) aryloxy group, it is preferable that it is C3-C20. Specifically, phenoxy group, 1-naphthyloxy group, 9-anthranyloxy group, 2-thienyloxy group, etc. are mentioned, for example.

As an alkylthio group, it is preferable that it is C1-C20. Specifically, methylthio group, ethylthio group, isopropylthio group, cyclohexylthio group, etc. are mentioned, for example.

As a (hetero) arylthio group, it is preferable that it is C3-C20. Specifically, a phenylthio group, 1-naphthylthio group, 9-anthranylthio group, 2-thienylthio group, etc. are mentioned, for example.

As a dialkylamino group, it is preferable that it is C2-C29. Specifically, a diethylamino group, a diisopropylamino group, a methyl ethyl amino group, etc. are mentioned, for example.

As an alkylarylamino group, it is preferable that it is C7-30. Specifically, a methylphenylamino group etc. are mentioned, for example.

As a diarylamino group, it is preferable that it is C12-30. Specifically, a diphenylamino group, a phenylnaphthylamino group, etc. are mentioned, for example.

Moreover, these substituents may further have a substituent. As a substituent in the case of having a substituent further, the said alkyl group, an aromatic ring group, an alkoxy group, a diarylamino group, etc. are mentioned, for example.

Below, the specific example of the anthracene derivative represented by said formula (V) is shown. However, the anthracene derivative represented by said formula (V) is not limited to these.

[Formula 18]

수송 hole transport layer material｝

In the present invention, the effect of reducing the concentrations of carbon dioxide, sulfur oxides and nitrogen oxides in the film formation environment of the hole transport layer will be described.

In an organic electroluminescent element, holes or electrons are injected from an electrode into an organic layer, and both are recombined in the light emitting layer to form an excited state and emit light. Organic electroluminescent devices using low molecules often have a charge transport layer for transporting charges between the light emitting layer and the electrode, rather than injecting carriers into the light emitting layer directly from the electrode. In forming this charge transport layer, if carbon dioxide, sulfur oxides, or nitrogen oxides are mixed in the charge transport layer, the charge is quenched, so that the transport is prevented. For this reason, it is thought that the carrier balance in a light emitting layer falls, and the efficiency of an organic electroluminescent element falls and a lifetime becomes short.

Therefore, the effect of this invention which reduces carbon dioxide, sulfur oxide, and nitrogen oxide concentration from the film-forming environment of a positive hole transport layer is large.

There is no restriction | limiting in particular as a hole transport layer material unless the effect of this invention is impaired. However, an aromatic amine compound is preferable as the hole transport layer material from the viewpoint of excellent hole transport ability.

Hereinafter, it describes about an aromatic amine compound.

<Aromatic amine compound>

As an aromatic amine compound, the high molecular compound containing the repeating unit represented by following formula (VI) is mentioned.

[Formula 19]

In formula (VI), m represents the integer of 0-3,

Ar ¹¹ and Ar ¹² each independently represent an aromatic ring group which may have a direct bond or a substituent, and Ar ¹³ to Ar ¹⁵ each independently represent an aromatic ring group which may have a substituent.

However, neither Ar ¹¹ nor Ar ¹² is a direct bond)

Here, an aromatic ring group represents an aromatic hydrocarbon group or an aromatic heterocyclic group.

As an aromatic hydrocarbon group which may have a substituent, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, for example And group derived from a 6-membered ring or a 2 to 5 condensed ring such as an acenaphthene ring, a fluoranthene ring and a fluorene ring.

As an aromatic heterocyclic group which may have a substituent, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carr Bazol ring, pyrrolomidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, phenanthridine ring, perimidine ring And group derived from a 5 or 6 membered ring or a 2 to 4 condensed ring, such as a quinazoline ring, a quinazolinone ring and an azulene ring.

In terms of solubility in solvents and heat resistance, Ar ¹¹ to Ar ¹⁵ each independently represent a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, Groups derived from rings selected from the group consisting of fluorene rings are preferred.

Moreover, as Ar <^11> -Ar <^15> , the bivalent group connected by the 1 type, or 2 or more types of ring selected from the said group by the direct bond or -CH = CH- group is preferable, A biphenylene group and terphenylene group are more preferable. Do.

There is no restriction | limiting in particular as a substituent which the aromatic ring group in Ar <^11> -Ar <^15> may have. As a substituent which the aromatic ring group in Ar <^11> -Ar <^15> may have, the 1 type (s) or 2 or more types chosen from the following <substituent group Z> are mentioned, for example.

<Substituent group Z>

Alkyl groups, such as a methyl group and an ethyl group, Preferably they are C1-C24, More preferably, C1-C12 alkyl group;

Alkenyl groups, such as a vinyl group, preferably C2-C24, More preferably, C2-C12;

Alkenyl groups, such as an ethynyl group, Preferably they are C2-C24, More preferably, C2-C12;

Alkoxy groups, such as a methoxy group and an ethoxy group, Preferably they are C1-C24, More preferably, C1-C12;

Phenoxy group, a naphthoxy group, a pyridyloxy group, etc. Preferably it is C4-C36, More preferably, C5-C24 aryloxy group;

Alkoxycarbonyl groups, such as a methoxycarbonyl group and an ethoxycarbonyl group, Preferably they are C2-C24, More preferably, C2-C12;

Dialkylamino groups, such as a dimethylamino group and diethylamino group, Preferably they are C2-C24, More preferably, C2-C12;

A diarylamino group having preferably 10 to 36 carbon atoms, more preferably 12 to 24 carbon atoms, such as a diphenylamino group, a totolylamino group, and an N-carbazolyl group;

An arylalkylamino group having preferably 6 to 36 carbon atoms, more preferably 7 to 24 carbon atoms such as a phenylmethylamino group;

Preferably an acetyl group, a benzoyl group, etc. Preferably it is a C2-C24, Preferably it is a C2-C12 acyl group;

Halogen atoms such as fluorine atom and chlorine atom;

Haloalkyl groups, such as a trifluoromethyl group, Preferably they are C1-C12, More preferably, C1-C6;

Alkylthio groups, such as a methylthio group and an ethylthio group, Preferably they are C1-C24, More preferably, C1-C12;

Preferably they are C4-C36, More preferably, C5-C24 arylthio group, such as a phenylthio group, a naphthylthio group, a pyridylthio group;

Preferably trimethylsilyl group, triphenylsilyl group, etc., C2-C36, More preferably, C3-C24 silyl group;

Preferably trimethylsiloxy group, a triphenyl siloxy group, etc. Preferably it is C2-C36, More preferably, C3-C24 siloxy group;

Cyano group;

Preferably they are C6-C36, More preferably, C6-C24 aromatic hydrocarbon groups, such as a phenyl group and a naphthyl group;

Preferably a thienyl group, a pyridyl group, etc., C3-C36, More preferably, C4-C24 aromatic heterocyclic group.

Each of the above substituents may further have a substituent, and examples thereof include the groups exemplified in the above <substituent group Z>.

As a molecular weight of the substituent which the aromatic ring group in Ar <^11> -Ar <^15> may have other than the insolubilizing group mentioned later, 500 or less are preferable including a substituted group, and 250 or less are more preferable.

As a substituent which the aromatic ring group in Ar <^11> -Ar <^15> may have in terms of solubility with respect to a solvent, a C1-C12 alkyl group and a C1-C12 alkoxy group are respectively independently preferable.

Further, when m is 2 or more, repeating units represented by the formula (VI) is imparted with two or more Ar ¹⁴ and Ar ^15. In that case, Ar <^14> and Ar <^{15> may} be same or different, respectively. Ar ¹⁴ and Ar ¹⁵ may be bonded to each other directly or through a linking group to form a cyclic structure.

In said formula (VI), m shows the integer of 0-3. m becomes like this. Preferably it is two or less. It is easy to synthesize | combine the monomer used as a raw material that m is two or less.

In addition, the hole transport layer material in the present invention preferably has an insolubilizing group as a substituent because the solubility in the solvent is lowered and the lamination is facilitated by wet film formation or the like on the hole transport layer.

An insolubilizing group is group which reacts by irradiation of a heat and / or active energy ray, etc. An insolubilizing group is group which has the effect of reducing the solubility to the organic solvent and water of the compound which has an insolubilizing group compared with before reaction by reaction.

It is preferable that this insolubilizing group is a group containing a dissociation group or a crosslinkable group.

When the high molecular compound containing the repeating unit represented by Formula (VI) has a group containing an insolubilizing group as a substituent, the substitution position of the insoluble group may be in the repeating unit represented by Formula (VI), and also formula (VI) You may have parts other than the repeating unit shown, for example by terminal group.

As an example of group containing a crosslinkable group as an insolubilizing group, what was illustrated to the following <crosslinkable group group Q> is mentioned. However, the group containing a crosslinkable group as an insolubilizing group which concerns on this invention is not limited to these.

<Cross bridge group Q>

[Formula 20]

(In formula, R <^81> -R <^85> represents a hydrogen atom or an alkyl group each independently. Ar <^81> represents the aromatic ring group which may have a substituent.)

Here, an aromatic ring group represents an aromatic hydrocarbon group or an aromatic heterocyclic group.

Moreover, the preferable specific example of group containing a dissociation group as an insoluble group is as follows. However, the group containing a dissociation group as an insolubilizing group which concerns on this invention is not limited to these.

The specific example in the case where group containing a dissociation group is bivalent is the same as group group G> containing the following <bivalent dissociation group.

<Group group G containing bivalent dissociation group>

[Formula 21]

The specific example in the case where a dissociation group is a monovalent group is the same as the following <monovalent dissociation group J>.

<Group group J containing monovalent dissociation group>

[Formula 22]

{solvent}

The solvent contained in the composition for organic electroluminescent elements used by this invention is used in order to form the layer containing an organic electroluminescent element material by wet film-forming. The solvent is usually a liquid having volatility.

The solvent is not particularly limited as long as it is a solvent in which the above-described organic electroluminescent element material, which is a solute, is dissolved well. As a preferable solvent, the following are mentioned.

For example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, methiylene, cyclohexylbenzene and tetralin; chlorobenzene and dichloro Halogenated aromatic hydrocarbons such as benzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phentol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxy Aromatic ethers such as toluene, 2,3-dimethylanisole, 2,4-dimethylanisole and diphenyl ether; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, benzoate and n-butyl benzoate Alicyclic ketones such as cyclohexanone, cyclooctanone and phencone; alicyclic alcohols such as cyclohexanol and cyclooctanol; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; aliphatic such as butanol and hexanol Alcohols; Ethylene Glycol Di And the like; butyl ether, ethylene glycol diethyl ether, an aliphatic ethers such as propylene glycol-1-monomethyl ether acetate (PGMEA).

Among these, Alkanes and aromatic hydrocarbons are preferable.

These solvents may be used individually by 1 type, and may use two or more types by arbitrary combinations and a ratio.

The boiling point of the solvent is usually 100 ° C or higher, preferably 150 ° C or higher, and more preferably 200 ° C or higher. It is preferable that the boiling point of a solvent is high at the time of wet film formation in the low risk of the film-forming stability by the solvent evaporation from the composition for organic electroluminescent elements falling.

Moreover, in order to obtain a more uniform film | membrane, it is preferable that a solvent evaporates at a suitable speed | rate from the liquid film immediately after film-forming. For this reason, the boiling point of a solvent is 80 degreeC or more normally, Preferably it is 100 degreeC or more, More preferably, it is 120 degreeC or more, Moreover, it is usually 270 degrees C or less, Preferably it is 250 degrees C or less, More preferably, the boiling point 230 It is below ℃.

{Furtherance}

The content of the above-mentioned organic electroluminescent device material in the composition for organic electroluminescent devices used in the present invention is usually at least 0.1% by weight, preferably at least 1% by weight, usually at most 99.99% by weight, preferably Is 99.9% by weight or less. The content of the organic electroluminescent device material of the composition is that the viscosity of the composition for organic electroluminescent devices is appropriate, the film formation workability is high, and the film thickness obtained by removing the solvent after film formation is sufficient, and the film formation is easy. It is preferable to set it as this range.

The content of the solvent in the composition for organic electroluminescent elements used in the present invention is preferably 10 parts by weight or more, more preferably 50 parts by weight or more, particularly preferably based on 100 parts by weight of the composition for organic electroluminescent devices. Preferably at least 80 parts by weight. On the other hand, with respect to 100 weight part of compositions for organic electroluminescent elements, Preferably it is 99.95 weight part or less, More preferably, it is 99.9 weight part or less, Especially preferably, it is 99.8 weight part or less. As for content of a solvent, the viscosity of the composition for organic electroluminescent elements is low, and many things are preferable at the point that film forming workability is easy. However, on the other hand, since it is easy to obtain the thickness of the film | membrane obtained by removing a solvent after film-forming, and easy to form film, few are preferable.

The organic electroluminescent element composition used by this invention can contain the other organic electroluminescent element material used in order to form the organic layer of an organic electroluminescent element other than the organic electroluminescent element material and solvent mentioned above.

However, the kind, composition, and concentration of the organic electroluminescent element material, the solvent, and other components in the composition for organic electroluminescent elements are appropriately set according to the kind of organic layer formed by the wet film-forming method. Conditions suitable for forming the light emitting layer and the hole transporting layer as the organic layer will be described later.

[Film Formation Process]

In the manufacturing method of the organic electroluminescent element of this invention, the organic layer of an organic electroluminescent element is formed by wet-forming in at least one of the above-mentioned film-forming environments 1-3 using the composition for organic electroluminescent elements mentioned above. .

In the present invention, the wet film forming method is, for example, a spin coating method, a dip coating method, a die coating method, a bar coating method, a blade coating method, a roll coating method, a spray coating method, a capillary coating method, an inkjet method, It means the method of wet-film-forming, such as screen printing, gravure printing, and flexographic printing. Among these film forming methods, the spin coating method, the spray coating method, and the inkjet method are preferable. This is because it is suitable for film-forming in the film-forming environments 1-3 which concerns on this invention.

In addition, below, the film formed by the wet film-forming method may be called "coating film."

In this invention, the film-forming process itself by a wet film-forming method can be performed in accordance with a conventional method.

Although the film forming temperature at the time of wet film forming is not limited, 10 degreeC or more is preferable and 13 degreeC or more is preferable at the point which the defect of a film | membrane by a crystal | crystallization and aggregation generate | occur | producing in the composition for organic electroluminescent elements mentioned above hardly occurs. 16 degreeC or more is more preferable. On the other hand, 50 degrees C or less is preferable, and 40 degrees C or less is more preferable.

The film forming surface to be formed by the wet film forming method is different depending on the type of organic layer to be formed. For example, when forming a light emitting layer as an organic layer, about the intermediate | middle layer, such as a positive electrode formed on the board | substrate of an organic electroluminescent element, or a hole injection layer or a hole transport layer formed as needed between an anode and a light emitting layer, Is formed. In addition, when forming a hole transport layer as an organic layer, a film is usually formed with respect to the intermediate | middle layer, such as an anode formed on the board | substrate of an organic electroluminescent element, or a hole injection layer formed as needed between an anode and a hole transport layer. .

[Drying process]

In the manufacturing method of the organic electroluminescent element of this invention, after forming into a film by the wet-film-forming method using the composition for organic electroluminescent elements, this coating film is dried. This drying step may be performed by any method as long as the film formed by the wet film formation method can be dried. Moreover, when the film | membrane formed by the wet film-forming method dries, it will become the thing which performed the drying process which concerns on this invention.

There is no restriction | limiting in particular about the working environment of this drying process. However, it is preferable to perform a drying process in the same environment as a film forming process, for the same reason as the above-mentioned film forming environment is preferable. Specifically, it is preferable to carry out under at least one of the above-mentioned film forming environments 1 to 3, and it is particularly preferable to carry out under the same temperature and humidity conditions.

In a drying process, heat drying is normally performed.

Examples of the heating means include a clean oven, hot plate, infrared ray, halogen heater, microwave irradiation and the like. Especially, a clean oven and a hot plate are preferable at the point which is easy to apply heat to the whole film | membrane uniformly.

The heating direction in the heating step is not limited as long as the effects of the present invention are not significantly impaired. For example, a heating film is heated from the lower surface (substrate side on which the organic layer is not formed) by mounting a film-forming substrate on a hot plate, and heating a coating film through the hot plate, for example. By putting a film-forming board | substrate into a method and a clean oven, the method of heating a coating film from the front, back, left, and right directions etc. are mentioned.

The heating temperature in the heating step is not particularly limited as long as the effect of the present invention is not significantly impaired. The heating temperature is usually 90 ° C. or higher, preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower. The heating temperature is preferably low in that the components are less likely to diffuse to other layers. On the other hand, the heating temperature is preferably high in that the remaining solvent is easily removed. Moreover, when it is a mixed solvent in which two or more types of solvents are contained in the composition for organic electroluminescent elements, it is preferable that at least 1 type is heated at the temperature more than the boiling point of the solvent.

The heating time in a heating process is not limited unless it remarkably inhibits the effect of this invention. Heating time becomes like this. Preferably it is 10 minutes or more, More preferably, it is 15 minutes or more, On the other hand, Preferably it is 4 hours or less, More preferably, it is 2 hours or less. By this heating, it becomes easy to insolubilize a coating film sufficiently. The heating time is preferably short in that the component is less likely to diffuse to other layers, and on the other hand, it is preferable in terms of homogeneity of the film.

[Film thickness]

In the manufacturing method of the organic electroluminescent element of this invention, the film thickness of the organic layer formed by the wet film-forming method differs according to the kind etc. of the organic layer formed. The film thickness of the organic layer is usually 3 nm or more, preferably 5 nm or more, and on the other hand, is usually 200 nm or less, preferably 100 nm or less. The film thickness is preferably thick because it is unlikely to cause defects in the film. On the other hand, the film thickness is preferably thin in that the driving voltage of the device is low.

In addition, a preferable film thickness differs according to the kind etc. of the organic layer to form. The film thickness of the light emitting layer and the hole transport layer as an organic layer is mentioned later.

[Storage process]

When the above-mentioned organic layer is formed by the wet film forming method, the element may be stored in a state in the middle of manufacturing due to the work process or the like after forming the organic layer until the layer on the organic layer is formed.

As described above, in the case of storing the device during film formation, the device during film formation has been stored under an environment in which oxygen and moisture are blocked, such as a nitrogen gas atmosphere, in order to prevent a decrease in life due to deterioration of the device under storage. For this reason, expensive storage facilities for storing elements have been required.

The inventors of the present invention also regard the storage environment of the device during the film formation in the same environment as the film forming step for the same reason as the above-described film formation environment, and thus, even in the case of storage in the air without using an expensive storage facility. It was found that deterioration of the device is unlikely to occur. That is, specifically, it is preferable to carry out storage in at least one of the above-mentioned film-forming environments 1-3, and it is especially preferable to carry out storing on the conditions of the same temperature and humidity.

In this case, the formation method of the organic layer formed in the outermost surface of the element stored is as having demonstrated in the manufacturing method of the organic electroluminescent element of this invention mentioned above. In addition, the organic layer in this case may not necessarily be formed in any of the above-mentioned film forming environments 1-3. That is, it is preferable to store in the same environment as the film forming process also about the storage environment in the case of storing what was formed under the environment which is not any of the above-mentioned film-forming environments 1-3. Moreover, as this organic layer to be stored, it is preferable that it is a light emitting layer and / or a hole transport layer similarly to the above.

In the case of storing the device in the middle of film formation under the same environment as any of the above-mentioned film forming environments 1 to 3, preferred environmental conditions, a method of preparing the environmental conditions, and the like are described in the above-described method of manufacturing the organic electroluminescent device of the present invention. Same as the description.

There is no restriction | limiting in particular in the temperature at the time of this storage. As for the temperature at the time of storage, 10 degreeC or more is preferable, 13 degreeC or more is more preferable, 16 degreeC or more is still more preferable, On the other hand, 50 degrees C or less is preferable, and 40 degrees C or less is more preferable.

The storage time is usually 6 hours or less, preferably 3 hours or less, and more preferably 1 hour or less. If it is in the said range, it is preferable at the point which productivity is high.

[2] organic electroluminescent devices

In the organic electroluminescent element of the present invention, the organic layer between the anode and the cathode of the organic electroluminescent element is formed by the wet film formation method according to the method for producing the organic electroluminescent element of the above-mentioned [1]. In the organic electroluminescent element of this invention, the organic layer formed by the manufacturing method of the organic electroluminescent element of this invention mentioned above, Preferably it is a light emitting layer or a hole transport layer, More preferably, it is a light emitting layer.

Below, the layer structure of the organic electroluminescent element manufactured by the method of this invention, its general formation method, etc. are demonstrated with reference to FIG.

1: is a schematic diagram of the cross section which shows the structural example of the organic electroluminescent element of this invention. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, 8 is an electron injection layer, 9 is a cathode, 10 Represents an organic electroluminescent element, respectively.

[Board]

The board | substrate 1 becomes a support body of an organic electroluminescent element. As the board | substrate 1, the plate of a quartz or glass, a metal plate, metal foil, a plastic film, a sheet, etc. are used. As for the board | substrate 1, the board of transparent synthetic resins, such as a glass plate and polyester, a polymethacrylate, a polycarbonate, polysulfone, is especially preferable. When using a synthetic resin substrate, it is preferable to pay attention to gas barrier property. That is, it is preferable to use the board | substrate with high gas barrier property in which the organic electroluminescent element which deteriorates by the outside air which passed through the board | substrate is hard to occur. Specifically, for example, a method of forming a dense silicon oxide film or the like on at least one side of the synthetic resin substrate to secure the gas barrier property and the like can be cited as one of the preferred methods.

[anode]

The anode 2 plays a role of hole injection into the layer on the light emitting layer 5 side.

This anode 2 is usually metal such as aluminum, gold, silver, nickel, palladium, platinum, metal oxides such as oxides of indium and / or tin, halogenated metals such as copper iodide, carbon black, or Conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline.

Formation of the anode 2 is usually performed by a sputtering method, a vacuum vapor deposition method, etc. in many cases. In the case of forming the anode 2 using metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, and the like, the conductive component is dispersed in a suitable binder resin solution. The anode 2 can also be formed by applying onto the substrate 1. In addition, in the case of a conductive polymer, a thin film can also be formed directly on the board | substrate 1 by electrolytic polymerization. In the case of the conductive polymer, it is also possible to form the positive electrode 2 by applying the conductive polymer on the substrate 1 (Appl. Phys. Lett., Vol. 60, p. 2711, 1992).

The anode 2 is usually a single layer structure, but may be a laminated structure composed of a plurality of materials as desired.

The thickness of the anode 2 is different depending on the required transparency and the like. When transparency is required, it is preferable to make the transmittance | permeability of visible light normally 60% or more, Preferably it is 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, it is usually 1000 nm or less, preferably 500 nm or less. When the anode 2 may be opaque, the thickness of the anode 2 is arbitrary. The anode 2 may be the same as the substrate 1. Further, different conductive materials may be laminated on the anode 2.

It is preferable that the surface of the anode 2 is removed by the ultraviolet (UV) / ozone treatment, oxygen plasma, argon plasma treatment, etc., to remove adhered impurities, and to adjust the ionization potential to improve hole injection properties.

[Hole injection layer]

The hole injection layer 3 is a layer which transports holes from the anode 2 to the light emitting layer 5. The hole injection layer 3 is usually formed on the anode 2.

The formation method of the hole injection layer 3 which concerns on this invention may be a vacuum vapor deposition method, a wet film-forming method, and there is no restriction | limiting in particular. As for the formation method of the hole injection layer 3 which concerns on this invention, the wet film-forming method is preferable from a dark spot reduction viewpoint.

The film thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and, on the other hand, usually 1000 nm or less, preferably 500 nm or less.

Formation of Hole Injection Layer by Wet Film Formation Method

In the case where the hole injection layer 3 is formed by wet film formation, a material for forming the hole injection layer 3 is usually mixed with an appropriate solvent (solvent for the hole injection layer) to form a film forming composition (for hole injection layer formation). Composition) is prepared. Then, the composition for forming the hole injection layer 3 is applied to a layer (typically, the anode 2) corresponding to the lower layer of the hole injection layer by a suitable method, and formed into a film, followed by drying to form a hole injection layer ( 3) form.

<Hole transporting compound>

The composition for forming a hole injection layer usually contains a hole transporting compound and a solvent as a constituent material of the hole injection layer 3.

The hole transporting compound may be a compound having hole transporting properties, which is usually used for the hole injection layer 3 of the organic electroluminescent element. The hole transporting compound may be a high molecular compound such as a polymer or a low molecular compound such as a monomer, but is preferably a high molecular compound.

As the hole transporting compound, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable from the viewpoint of the charge injection barrier from the anode 2 to the hole injection layer 3. Examples of hole-transporting compounds include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl derivatives, compounds in which tertiary amines are linked with fluorene groups, hydrazone derivatives, silazane derivatives, Silanamine derivatives, phosphamine derivatives, quinacridone derivatives, polyaniline derivatives, polypyrrole derivatives, polyphenylenevinylene derivatives, polythienylenevinylene derivatives, polyquinoline derivatives, polyquinoxaline derivatives, carbon and the like.

In addition, in this invention, if an aromatic amine derivative is taken as an example, the derivative contains the compound which makes aromatic amine itself and aromatic amine main frame | skeleton, and a polymer may be sufficient as it.

The hole transporting compound used as the material of the hole injection layer 3 may contain any one of these compounds alone, or may contain two or more thereof. When it contains 2 or more types of hole transport compounds, the combination and ratio are arbitrary, but it is preferable to use together 1 type (s) or 2 or more types of aromatic tertiary amine high molecular compounds, and 1 type (s) or 2 or more types of other hole transport compounds. .

Among the above examples, in view of amorphousness and transmittance of visible light, an aromatic amine compound is preferable, and an aromatic tertiary amine compound is particularly preferable. Here, an aromatic tertiary amine compound is a compound which has an aromatic tertiary amine structure, and also includes the compound which has group derived from aromatic tertiary amine.

The kind of aromatic tertiary amine compound is not particularly limited. The aromatic tertiary amine compound is more preferably a polymer compound having a weight average molecular weight of 1000 or more and 1000000 or less (polymerizable compound to which repeating units are linked) in that uniform light emission due to the surface smoothing effect is easily obtained. Preferred examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following Formula (I).

[Formula 23]

(In Formula (I), Ar <^1> -Ar <^5> respectively independently represents the aromatic ring group which may have a substituent. Z <^b> represents the coupling group chosen from the following group of coupling groups. Moreover, in Ar <^1> -Ar <^5> . , Two groups bonded to the same N atom may be bonded to each other to form a ring.)

<Connector group>

[Formula 24]

(In each said formula, Ar <^6> -Ar <^16> respectively independently represents the aromatic ring group which may have a substituent. R <^5> and R <^6> respectively independently represents a hydrogen atom or an arbitrary substituent. Here, an aroma A cyclic group represents an aromatic hydrocarbon group or an aromatic heterocyclic group)

As the aromatic ring group for Ar ¹ to Ar ¹⁶ , a group derived from a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, a pyridine ring is preferable in view of solubility, heat resistance, hole injection and transportability of a high molecular compound, and a benzene ring, More preferred are groups derived from naphthalene rings.

The aromatic ring group of Ar ¹ to Ar ¹⁶ may further have a substituent. As a molecular weight of a substituent, 400 or less are usually preferable, and especially 250 or less are preferable. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an aromatic ring group, etc. are preferable.

When R <^5> and R <^6> are arbitrary substituents, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic ring group etc. are mentioned as this substituent.

As a specific example of the aromatic tertiary amine high molecular compound which has a repeating unit represented by Formula (I), the thing of international publication 2005/089024, etc. are mentioned.

As the hole transporting compound, a conductive polymer (PEDOT / PSS) formed by polymerizing 3,4-ethylenedioxythiophene (3,4-ethylenedioxythiophene), which is a derivative of polythiophene, in a high molecular weight polystyrenesulfonic acid is also preferable. Moreover, what capped the terminal of this polymer by methacrylate etc. may be sufficient.

The hole transporting compound may be a crosslinking compound described in the section of the following [hole transporting layer]. The film formation method in the case of using the crosslinkable compound is also the same as the method described in the section of the following [hole transport layer].

The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired. The concentration of the hole-transporting compound is preferably small in that film thickness non-uniformity is unlikely to occur. On the other hand, the concentration of the hole-transporting compound is preferably large in that defects do not easily occur in the hole injection layer formed. Specifically, the concentration of the hole transporting compound is, in terms of uniformity of film thickness, usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and usually 70% by weight. % Or less, Preferably it is 60 weight% or less, More preferably, it is 50 weight% or less.

<Electron water-soluble compound>

It is preferable that the composition for hole injection layer formation contains the electron accepting compound as a constituent material of the hole injection layer 3.

The electron-accepting compound preferably has a oxidizing power and a compound having the ability to accept one electron from the above-mentioned hole transporting compound. Specifically, the compound whose electron affinity is 4 eV or more is preferable, and the compound which is 5 eV or more is more preferable.

Examples of such an electron-accepting compound include one selected from the group consisting of triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, salts of arylamines and Lewis acids And 2 or more types of compounds, etc. are mentioned. More specifically, onium salt in which organic groups, such as 4-isopropyl-4'-methyldiphenyl iodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate, were substituted (international publication 2005 / 089024); inorganic compounds of high-valent valences such as iron (III) chloride (JP-A-11-251067) and ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene and tris (pentafluorophenyl) borane Aromatic boron compounds, such as (Unexamined-Japanese-Patent No. 2003-31365); Fullerene derivative; Iodine; Polystyrene sulfonate ion, Sulfonic acid ion, such as alkylbenzene sulfonic acid ion, camphor sulfonic acid ion, etc. are mentioned.

These electron-accepting compounds can improve the electrical conductivity of the hole injection layer 3 by oxidizing the hole transporting compound.

The content of the hole-transporting compound of the electron-accepting compound in the hole injection layer 3 or the hole injection layer-forming composition is usually 0.1 mol% or more, preferably 1 mol% or more. On the other hand, it is 100 mol% or less normally, Preferably it is 40 mol% or less.

<Other structural materials>

As a material of the hole injection layer 3, in addition to the above-mentioned hole transporting compound and an electron accepting compound, you may contain another component, unless the effect of this invention is remarkably impaired. Examples of the other components include various light emitting materials, electron transporting compounds, binder resins, coatability improving agents and the like. In addition, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

<Solvent>

It is preferable that at least 1 sort (s) of the solvent of the composition for hole injection layer formation used for a wet film-forming method is a compound which can melt | dissolve the structural material of the hole injection layer 3 mentioned above. The boiling point of the solvent is preferably high in that drying is too fast and the film quality is unlikely to be lowered. On the other hand, low temperature drying is possible and in that it is unlikely to affect other layers or substrates, Low is desirable. Therefore, the boiling point of a solvent is 110 degreeC or more normally, Preferably it is 140 degreeC or more, More preferably, it is 200 degreeC or more, On the other hand, It is preferable that it is 400 degrees C or less normally, especially 300 degrees C or less.

As a solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an amide solvent, etc. are mentioned, for example.

As an ether solvent, For example, Aliphatic ethers, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1, 2- dimethoxy benzene, 1, 3- Aromatic ethers such as dimethoxybenzene, anisole, phentol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole Can be.

Examples of the ester solvents include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, benzoate benzoate and n-butyl benzoate.

As an aromatic hydrocarbon solvent, for example, toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, methylnaphthalene Etc. can be mentioned.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

In addition, dimethyl sulfoxide etc. can also be used.

These solvents may use only 1 type, and may use 2 or more types by arbitrary combinations and a ratio.

<Film formation method>

After preparing the composition for forming a hole injection layer, the composition is applied to a layer corresponding to the lower layer of the hole injection layer 3 (typically, the anode 2) by a wet film formation method, and then formed into a hole by drying. The injection layer 3 is formed.

As for the temperature in a coating process, 10 degreeC or more is preferable and 50 degreeC or less is preferable at the point which the defect of a film | membrane by a crystal | crystallization in a composition hardly produces.

The relative humidity in the coating step is not limited as long as the effect of the present invention is not significantly impaired. The relative humidity is usually 0.01 ppm or more, usually 80% or less.

After application of the composition for forming a hole injection layer, the film of the composition for forming a hole injection layer is usually dried by heating or the like. Examples of the heating means used in the heating step include ovens, hot plates, infrared rays, halogen heaters, microwave irradiation, and the like. Especially, an oven and a hotplate are preferable at the point which is easy to apply heat to the whole film | membrane uniformly.

Heating temperature in a heating process is arbitrary, as long as the effect of this invention is not impaired remarkably. As for the heating temperature, the temperature more than the boiling point of the solvent used for the composition for hole injection layer formation is preferable. Moreover, when two or more types of solvents are contained in a hole injection layer, it is preferable to heat at the temperature more than the boiling point of the at least one type of solvent. In consideration of the rising of the boiling point of the solvent, in the heating step, it is preferable to heat at 120 ° C or higher, preferably 410 ° C or lower.

In a heating process, when heating temperature is more than the boiling point of the solvent of the composition for positive hole injection layer formation, and sufficient insolubilization of a coating film occurs, heating time is not limited. The heating time is preferably 10 seconds or more, and usually 180 minutes or less. The heating time is preferably short in that the components of the other layers are less likely to diffuse, and preferably longer in that the hole injection layer is more homogeneous. You may divide and heat two times.

In the wet film formation of the hole injection layer 3, wet film formation may be performed in any of the above-described film forming environments 1 to 3, but in general, the effect of the film forming environment of the hole injection layer on the device life is determined by the light emitting layer. Since it is not as large as a film-forming environment, the film-forming method of the hole injection layer 3 may be wet film-forming in normal air | atmosphere.

｝ Formation of Hole Injection Layer 3 by Vacuum Evaporation Method 법

When forming the hole injection layer 3 by vacuum vapor deposition, it can form in the following procedures, for example. One or two or more kinds of constituent materials of the hole injection layer 3 (hole transporting compound, electron-accepting compound, etc. described above) are placed in a crucible provided in a vacuum vessel (when two or more kinds of materials are used, each crucible is placed in a crucible. Put). Using a vacuum pump, the vacuum vessel is evacuated to about 10 ^-4 Pa. The crucible is heated (by heating each crucible when using two or more kinds of materials) to control and evaporate the amount of evaporation (if using two or more kinds of materials, each evaporation is independently controlled and evaporated). On the anode 2 on the substrate 1 placed facing the crucible, the hole injection layer 3 is formed. In the case of using two or more kinds of materials, the mixture may be placed in a crucible and heated and evaporated to form the hole injection layer 3.

The degree of vacuum at the time of vapor deposition is not limited unless it remarkably impairs the effect of this invention. The degree of vacuum during deposition is usually at least 0.1 × 10 ⁻⁶ Torr (0.13 × 10 ⁻⁴ Pa) and usually at most 9.0 × 10 ⁻⁶ Torr (12.0 × 10 ⁻⁴ Pa). The deposition rate is not limited as long as the effect of the present invention is not significantly impaired. The deposition rate is usually at least 0.1 mW / sec, usually at most 5.0 mW / sec. The film formation temperature at the time of vapor deposition is not limited, unless the effect of this invention is impaired remarkably. Film-forming is preferably performed at 10 degreeC or more, Preferably it is 50 degrees C or less.

[Hole transport layer]

The hole transport layer 4 can be formed on the hole injection layer 3 when the hole injection layer 3 is present, and on the anode 2 when the hole injection layer 3 is not provided. The organic electroluminescent element of the present invention may have a configuration in which the hole transport layer 4 is omitted.

The formation method of the hole transport layer 4 may be a vacuum vapor deposition method, a wet film-forming method, and there is no restriction | limiting in particular. From the viewpoint of dark spot reduction, the hole transport layer 4 is preferably formed by a wet film formation method, and in particular, it is preferable to perform wet film formation under any of the above-described film formation environments 1 to 3 according to the method of the present invention.

As a material for forming the hole transport layer 4, a material having high hole transportability and capable of efficiently transporting the injected holes is preferable. Therefore, a material having a small ionization potential, high transparency to visible light, high hole mobility, excellent stability, and hardly causing impurities to be trapped during production or use is preferable. In addition, when the hole transport layer 4 is in contact with the light emitting layer 5, it is preferable not to extinguish the light emission from the light emitting layer 5 or to form an exciplex between the light emitting layer 5 to lower the efficiency. Do.

As a material of such a hole transport layer 4, the material conventionally used as a constituent material of the hole transport layer 4 may be sufficient. Specifically, what was illustrated as a hole-transport compound used for the above-mentioned hole injection layer 3, etc. are mentioned, for example. Further, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, silol derivatives, oligoti Offen derivatives, condensed polycyclic aromatic derivatives, metal complexes and the like.

In addition, for example, polyvinylcarbazole derivatives, polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylene Vinylene derivatives, polysiloxane derivatives, polythiophene derivatives, poly (p-phenylenevinylene) derivatives, and the like. These may be any of an alternating copolymer, a random polymer, a block polymer, or a graft copolymer. Moreover, the polymer which has a branch in a principal chain and three or more terminal parts, or what is called a dendrimer may be sufficient.

Especially, a polyarylamine derivative and a polyarylene derivative are preferable.

As a polyarylamine derivative, it is preferable that it is a polymer containing the repeating unit represented by following formula (II). It is especially preferable that it is a polymer which consists of a repeating unit represented by following formula (II), and in this case, Ar ^a or Ar ^b may differ in each of a repeating unit.

[Formula 25]

(In Formula (II), Ar ^a and Ar ^b each independently represent an aromatic ring group which may have a substituent.) Here, the aromatic ring group represents an aromatic hydrocarbon group or an aromatic heterocyclic group.

As an aromatic hydrocarbon group which may have a substituent of Ar ^a and Ar ^b , for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene 6-membered monocyclic or groups derived from 2 to 5 condensed rings, such as rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, and groups in which these rings are linked by two or more direct bonds; Can be mentioned.

As an aromatic heterocyclic group which may have a substituent, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carr Bazol ring, pyrrolomidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cynoline ring, quinoxaline ring, phenanthridine ring, perimidine ring Or groups derived from 5- or 6-membered rings or from 2 to 4 condensed rings, such as quinazoline rings, quinazolinone rings, and azulene rings, and these rings are connected by two or more direct bonds. Is group and the like can be made.

In terms of solubility and heat resistance, Ar ^a and Ar ^b each independently include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring Groups derived from a ring or a benzene ring selected from the group in which two or more rings are connected (for example, a biphenyl group (biphenyl group) or terphenylene group (terphenylene group)) are preferable.

Especially, the group (phenyl group) derived from a benzene ring, the group (biphenyl group) by which the benzene ring connects 2 rings, and the group (fluorenyl group) derived from a fluorene ring are preferable.

Examples of the substituent which the aromatic ring group in Ar ^a and Ar ^b may have include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a dialkylamino group, a diarylamino group, an acyl group, a halogen atom, Haloalkyl group, alkylthio group, arylthio group, silyl group, siloxy group, cyano group, aromatic hydrocarbon group, aromatic heterocyclic group and the like.

As a polyarylene derivative, the polymer etc. which have arylene groups, such as an aromatic ring group which may have a substituent illustrated as Ar ^a and Ar ^b in the said Formula (II), in the repeating unit are mentioned.

As a polyarylene derivative, the polymer which has a repeating unit which consists of a following formula (V-1) and / or a following formula (V-2) is preferable.

[Formula 26]

(In formula (V-1), R ^a , R ^b , R ^c and R ^d are each independently an alkyl group, an alkoxy group, a phenylalkyl group, a phenylalkoxy group, a phenyl group, a phenoxy group, an alkylphenyl group, an alkoxyphenyl group or an alkyl. A carbonyl group, an alkoxycarbonyl group, or a carboxyl group, t and s each independently represent an integer of 0 to 3. When t or s is 2 or more, a plurality of R ^a or R ^b contained in one molecule are the same; May be different or may be adjacent to R ^a or R ^b to form a ring)

[Formula 27]

(In formula (V-2), R ^e and R ^f are each independently the same meaning as R ^b or R ^{a in} the formula (V-1). R and u are each independently 0. It represents the integer of-3. When r or u is 2 or more, some R <^e> and R <^f> contained in 1 molecule may be same or different, and may form the adjacent R <^e> or R <^f> ring. X represents an atom or an atomic group constituting a 5-membered ring or a 6-membered ring)

Specific examples of X are -O-, -BR-, -NR-, -SiR _2- , -PR-, -SR-, -CR ₂ -or a group formed by bonding thereof. In addition, R represents a hydrogen atom or an arbitrary organic group. The organic group in this invention is group containing at least 1 carbon atom.

Moreover, as a polyarylene derivative, in addition to the repeating unit which consists of said Formula (V-1) and / or said Formula (V-2), it is preferable to have a repeating unit further represented by following formula (V-3). Do.

[Formula 28]

(In Formula (V-3), Ar ^c to Ar ^j each independently represent an aromatic ring group which may have a substituent. Ｖ and w each independently represent 0 or 1).

Specific examples of Ar ^c to Ar ^j are the same as those of Ar ^a and Ar ^b in the formula (II).

Specific examples of the formulas (V-1) to (V-3) and specific examples of the polyarylene derivatives include those described in JP-A-2008-98619.

In the case of forming the hole transport layer 4 by the wet film formation method, the composition for forming a hole transport layer can be prepared in the same manner as the above method for forming the hole injection layer 3, and then formed by heating and drying after wet film formation.

The composition for forming a hole transporting layer contains a solvent in addition to the hole transporting compound described above. The solvent used is the same as the solvent used for the said composition for hole injection layer formation. Moreover, film forming conditions, heat drying conditions, etc. are also the same as the case of formation of the hole injection layer 3.

Also in the case of forming the hole transport layer 4 by the vacuum vapor deposition method, the film forming conditions and the like are the same as in the case of the hole injection layer 3 formation.

The hole transport layer 4 may contain various light emitting materials, an electron transport compound, a binder resin, a coatability improving agent, etc. in addition to the said hole transport compound.

The hole transport layer 4 may be a layer formed by crosslinking a crosslinkable compound. A crosslinkable compound is a compound which has a crosslinkable group, and forms a net polymer compound by crosslinking.

Examples of this crosslinkable group include groups derived from cyclic ethers such as oxetane and epoxy; derived from unsaturated double bonds such as vinyl group, trifluorovinyl group, styryl group, acryl group, methacryloyl and cinnamoyl. Group; group derived from benzocyclobutene, etc. are mentioned.

The crosslinkable compound may be any of a monomer, an oligomer, and a polymer. The crosslinkable compound may have only 1 type and may have 2 or more types by arbitrary combinations and a ratio.

As a crosslinkable compound, it is preferable to use the hole-transporting compound which has a crosslinkable group. Examples of the hole transporting compound include those exemplified above. As these hole-transporting compounds, what has a crosslinkable group couple | bonded with a main chain or a side chain with respect to these hole-transporting compounds is mentioned. In particular, the crosslinkable group is preferably bonded to the main chain via a linking group such as an alkylene group. Moreover, especially as a hole-transporting compound, it is preferable that it is a polymer containing a repeating unit which has a crosslinkable group, and a crosslinkable group is directly or a linking group in said Formula (II) and Formula (V-1)-(V-3). Preference is given to polymers having repeating units bonded through.

Examples of the hole-transporting compound include nitrogen-containing aromatic compound derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives, phthalocyanine derivatives and porphyrin derivatives; Derivatives; silol derivatives; oligothiophene derivatives, condensed polycyclic aromatic derivatives, metal complexes and the like. Among them, nitrogen-containing aromatic derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives and carbazole derivatives; triphenylamine derivatives, silol derivatives, condensed polycyclic aromatic derivatives, metals Complexes are preferred, and triphenylamine derivatives are more preferred.

In order to bridge | crosslink a crosslinkable compound and to form the hole transport layer 4, the composition for hole transport layer formation which melt | dissolved or disperse | distributed a crosslinkable compound in a solvent is normally prepared, this is formed into a film by wet film-forming, and it crosslinks.

In addition to the crosslinkable compound, the composition for forming a hole transport layer may contain an additive that promotes a crosslinking reaction. Examples of the additives for promoting the crosslinking reaction include polymerization initiators and polymerization accelerators such as alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds and onium salts; condensed polycyclic hydrocarbons and porphyrin compounds And photosensitizers, such as a diaryl ketone compound; These etc. are mentioned.

Moreover, the composition for hole transport layer formation may contain coating property improving agents, such as a leveling agent and an antifoamer, an electron-accepting compound, binder resin, etc.

The composition for forming a hole transporting layer usually contains 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and usually 50% by weight or less, preferably 20% by weight. Hereinafter, More preferably, it contains 10 weight% or less.

After forming a composition for forming a hole transport layer containing a crosslinkable compound at such a concentration on a lower layer (usually a hole injection layer 3), the crosslinkable compound is formed by irradiation with active energy such as heating and / or light. Crosslinking to form a net polymer compound.

The conditions, such as temperature and humidity at the time of film-forming, are the same as that of the wet film-forming of the said hole injection layer.

The heating method after film-forming is not specifically limited. As heating temperature conditions, it is 120 degreeC or more normally, Preferably it is 400 degrees C or less.

As heating time, it is 1 minute or more normally, Preferably it is 24 hours or less. It does not specifically limit as a heating means. Heating is performed by means, such as mounting a laminated body which has a layer formed into a film on a hotplate, or heating in an oven. For example, conditions, such as heating 120 degreeC or more and 1 minute or more on a hotplate, can be used.

In the case of crosslinking by irradiation of active energy such as light, a method of directly irradiating ultraviolet, visible and infrared light sources such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a halogen lamp and an infrared lamp, or a mask aligner incorporating the light source described above And the method of irradiating using a conveyor type light irradiation apparatus, etc. are mentioned. In active energy irradiation other than light, the apparatus which irradiates the microwave which generate | occur | produced with the magnetron, the method of irradiating using a so-called microwave oven, etc. are mentioned, for example. As irradiation time, it is preferable to set the conditions required in order to reduce the solubility of a film | membrane. Irradiation time is 0.1 second or more normally, Preferably it is 10 hours or less.

You may perform active energy irradiation, such as a heating and light, respectively, individually or in combination. When combining, the order to implement is not specifically limited.

The film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and on the other hand, is usually 300 nm or less, preferably 100 nm or less.

[Light emitting layer]

In the case where the hole injection layer 3 or the hole transport layer 4 is formed, the light emitting layer 5 is usually formed on the hole transport layer 4. The light emitting layer 5 is a layer which is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between electrodes provided with an electric field, and serves as a main light emitting source.

｝ Material of light emitting layer 층

The light emitting layer 5 contains a material (light emitting material) having at least light emitting property as its constituent material. The light emitting layer 5 preferably contains a compound having a property of transporting holes (hole transporting compound) or a compound having a property of transporting electrons (electron transporting compound) as its constituent material. In the light emitting layer 5, a light emitting material may be used as a dopant material, and a hole transporting compound, an electron transporting compound, or the like may be used as the host material. There is no restriction | limiting in particular about a luminescent material. The light emitting material emits light at a desired light emission wavelength, and a material having good luminous efficiency may be used. The light emitting layer 5 may contain the other component in the range which does not significantly inhibit the effect of this invention. In addition, when forming the light emitting layer 5 by the wet film-forming method, it is preferable to use the material of low molecular weight in all.

<Luminescent material>

Arbitrary well-known materials are applicable as a luminescent material. The light emitting material may be, for example, a fluorescent light emitting material or a phosphorescent light emitting material. The light emitting material is preferably a phosphorescent light emitting material in view of internal quantum efficiency. In addition, blue may use a fluorescent light emitting material, and green and red may use a combination of plural kinds of light emitting materials, such as using a phosphorescent light emitting material.

Moreover, it is preferable to reduce symmetry and rigidity of the molecule | numerator of a light emitting material, or to introduce lipophilic substituents, such as an alkyl group, into a light emitting material in order to improve the solubility to the solvent of a light emitting material.

Hereinafter, examples of the fluorescent light emitting material among the light emitting materials will be given. However, the fluorescent dye is not limited to the following examples.

Examples of fluorescent light emitting materials (blue fluorescent dyes) that give blue light emission include naphthalene, perylene, pyrene, chrysene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Can be.

Roneun fluorescent light emitting material (green fluorescent dye) to give the green light emission, for example, there may be mentioned quinacridone derivatives, coumarin derivatives, aluminum complexes such as _{Al (C 9 H 6 NO)} 3 and the like.

As a fluorescent light emitting material (yellow fluorescent dye) which gives yellow light emission, rubrene, a perimidone derivative, etc. are mentioned, for example.

Examples of fluorescent light emitting materials (red fluorescent dyes) that give red light emission include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) -based compounds, benzopyran derivatives, Rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene and the like.

As a phosphorescence emitting material, for example, in the manufacturing method of the organic electroluminescent element of this invention WHEREIN: As an example of the organic electroluminescent element material in the composition for organic electroluminescent elements used for formation of the organic layer by a wet-film-forming method, Organometallic complexes; and the like.

The molecular weight of the compound used as a luminescent material is arbitrary unless the effect of this invention is impaired remarkably. The molecular weight of the light emitting material is preferably high in terms of excellent heat resistance, hardly generating gas, excellent film quality when a film is formed, and morphological change of the organic electroluminescent device due to migration or the like. . On the other hand, since the molecular weight of a light emitting material is easy to refine | purify an organic compound, and is easy to melt | dissolve in a solvent for a short time, a small thing is preferable. Therefore, the molecular weight is specifically 10000 or less, Preferably it is 5000 or less, More preferably, it is 4000 or less, More preferably, it is 3000 or less, On the other hand, 100 or more, Preferably it is 200 or more More preferably, it is 300 or more, More preferably, it is 400 or more.

In addition, any 1 type may be used for the above-mentioned light emitting material, and may use 2 or more types together by arbitrary combinations and a ratio.

The ratio of the luminescent material in a light emitting layer is arbitrary as long as the effect of this invention is not impaired remarkably. Although the ratio of the luminescent material in a light emitting layer is many in terms of luminous efficiency, it is preferable, On the other hand, a small thing is preferable in the point that light emission nonuniformity hardly arises. Therefore, the ratio of the luminescent material in a light emitting layer is 0.05 weight% or more normally, and is 35 weight% or less normally. In addition, when using 2 or more types of luminescent materials together, it is preferable to make content of these sum totals fall in the said range.

<Hole transporting compound>

The light emitting layer 5 may contain a hole transporting compound as its constituent material. Here, as an example of the low molecular weight hole transporting compound among the hole transporting compounds, various compounds exemplified as (low molecular weight hole transporting compound) in the hole injection layer described above can be mentioned. In addition, examples of the low molecular weight hole transport compound include two or more tertiary groups represented by, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl. Aromatic diamines containing amines and at least two condensed aromatic rings substituted with nitrogen atoms (JP-A-5-234681), 4,4 ', 4' '-tris (1-naphthylphenylamino) triphenylamine Aromatic amine compounds having a star burst structure such as (Journal of Luminescence, 1997, Vol. 72-74, pp. 985), aromatic amine compounds consisting of tetramers of triphenylamine (Chemical Communications, 1996, pp.2175 ), Spiro compounds such as 2,2 ', 7,7'-tetrakis- (diphenylamino) -9,9'-spirobifluorene (Synthetic Metals, 1997, Vol. 91, pp.209), etc. Can be mentioned.

In addition, in the light emitting layer 5, only 1 type may be used for a hole-transporting compound, and may use 2 or more types together by arbitrary combinations and a ratio.

The proportion of the hole transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired. The ratio of the hole-transporting compound is preferably large in that it is less likely to be affected by a short circuit. On the other hand, the smaller one is preferable in that the film thickness unevenness is unlikely to occur. The proportion of the hole transporting compound in the light emitting layer 5 is usually at least 0.1% by weight, usually at most 65% by weight. In addition, when using 2 or more types of hole transport compounds together, it is preferable to make content of these sum totals fall in the said range.

<Electron transport compound>

The light emitting layer 5 may contain an electron transporting compound as its constituent material. Herein, examples of the low molecular weight electron transport compound among the electron transport compound include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND) and 2,5-bis (6). '-(2', 2'-bipyridyl))-1,1-dimethyl-3,4-diphenylsilol (PyPySPyPy) or vasophenanthroline (BPhen) or 2,9-dimethyl-4 , 7-diphenyl-1,10-phenanthroline (BCP, vasocuproin), 2- (4-biphenylyl) -5- (p-tert-butylphenyl) -1,3,4-oxadia Sol (tBu-PBD), 4,4'-bis (9-carbazole) -biphenyl (CBP), etc. are mentioned. In addition, in a light emitting layer, only 1 type may be used for an electron carrying compound, and may use 2 or more types together by arbitrary combinations and a ratio.

The ratio of the electron transport compound in the light emitting layer 5 is arbitrary unless the effect of this invention is impaired remarkably. Although the ratio of an electron carrying compound is large in the point which is hard to be influenced by a short circuit, it is preferable in the point which is difficult to produce a film thickness nonuniformity, and a small thing is preferable. The proportion of the electron transporting compound in the light emitting layer 5 is usually 0.1% by weight or more and usually 65% by weight or less. In addition, when using 2 or more types of electron transport compounds together, it is preferable to make content of these sum totals fall in the said range.

｝ Formation of light emitting layer｝

When forming the light emitting layer 5 by the wet film forming method which concerns on this invention, the said material can be melt | dissolved in a suitable solvent, the composition for light emitting layer formation can be prepared, and can be formed by wet film-forming using it. It is preferable to perform wet film-forming in any one of the above-mentioned film-forming environments 1-3.

As a solvent for a light emitting layer which makes the light emitting layer 5 contain in the composition for light emitting layer formation for forming by the wet film-forming method which concerns on this invention, arbitrary things can be used as long as formation of a light emitting layer is possible. Preferable examples of the solvent for the light emitting layer are the same as the solvents described for the composition for forming a hole injection layer.

The ratio of the solvent for a light emitting layer with respect to the composition for light emitting layer formation for forming a light emitting layer is arbitrary, as long as the effect of this invention is not impaired remarkably. The ratio of the solvent for a light emitting layer with respect to the composition for light emitting layer formation is 30 weight% or more normally, Usually 99.9 weight% or less. In addition, when mixing 2 or more types of solvents as a solvent for a light emitting layer, it is preferable to make the total amount of these solvents satisfy | fill this range.

The total concentration of solids such as light-emitting materials, hole-transporting compounds, electron-transporting compounds, etc. in the light-emitting layer-forming composition is preferably low in that film thickness non-uniformity is unlikely to occur. High is preferred. The total concentration of the solid content is usually 0.01% by weight or more and usually 70% by weight or less.

The light emitting layer 5 is formed by wet-forming the composition for light emitting layer formation, and then drying the obtained coating film and removing a solvent. The formation method of the light emitting layer 5 is specifically the same as the method described in formation of the said hole injection layer 4. The method of the wet film forming method is not limited as long as the effect of the present invention is not significantly impaired, and any of the methods described above can be used.

The film thickness of the light emitting layer 5 is arbitrary as long as the effect of this invention is not impaired remarkably. Although the film thickness of the light emitting layer 5 is preferable in the point which a defect does not generate | occur | produce in a film | membrane, on the other hand, a thin thing is preferable in the point which is easy to lower a drive voltage. The film thickness of the light emitting layer 5 is usually 3 nm or more, preferably 5 nm or more, and is usually in the range of 200 nm or less, preferably 100 nm or less.

[Hole blocking layer]

You may form the hole blocking layer 6 between the light emitting layer 5 and the electron injection layer 8 mentioned later. The hole blocking layer 6 is a layer which is normally laminated on the light emitting layer 5 so as to be in contact with the interface on the side of the cathode 9 of the light emitting layer 5.

The hole blocking layer 6 serves to prevent holes traveling from the anode 2 from reaching the cathode 9 and to efficiently transport electrons injected from the cathode 9 toward the light emitting layer 5. Has

The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), excitation triplet level (T1) And a high one. As a material of the hole-blocking layer 6 which satisfy | fills such conditions, bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinoli), for example Mixed ligand complexes such as norato) (triphenylsilanolato) aluminum, bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum 2 Styryl compounds such as metal complexes such as nuclear metal complexes and distyryl biphenyl derivatives (JP-A-11-242996) and 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butyl Triazole derivatives such as phenyl) -1,2,4-triazole (JP-A-7-41759), phenanthroline derivatives such as vasocuproin (JP-A-10-79297), and the like. Can be mentioned. Moreover, the compound which has at least 1 the pyridine ring by which 2, 4, 6 positions were described in international publication 2005/022962 is also preferable as a material of the hole-blocking layer 6.

In addition, only 1 type may be used for the material of the hole-blocking layer 6, and 2 or more types may be used together by arbitrary combinations and a ratio.

There is no restriction | limiting in the formation method of the hole blocking layer 6. Therefore, it can form by the wet film-forming method, the vapor deposition method, or another method.

The film thickness of the hole blocking layer 6 is arbitrary unless the effect of this invention is remarkably impaired. The film thickness of the hole blocking layer 6 is usually at least 0.3 nm, preferably at least 0.5 nm, and on the other hand, is usually at most 100 nm, preferably at most 50 nm.

[Electron transport layer]

You may form the electron carrying layer 7 between the light emitting layer 5 and the electron injection layer 8 mentioned later.

The electron transport layer 7 is a layer formed for the purpose of further improving the luminous efficiency of the device. The electron transport layer 7 is formed of a compound capable of transporting electrons injected from the cathode 9 in the direction of the light emitting layer 5 efficiently between electrodes provided with an electric field.

As an electron transport compound used for the electron carrying layer 7, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and it has a high electron mobility, and conveys the injected electron efficiently Use compounds that can. As a compound satisfying such conditions, for example, metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393) and metal complexes of 10-hydroxybenzo [h] quinoline , Oxadiazole derivatives, distyrylbiphenyl derivatives, silol derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzenes (US Patent 5645948 specification), quinoxaline compound (JP-A-6-207169), phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N'- dicyano anthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, etc. are mentioned.

In addition, only 1 type may be used for the material of the electron carrying layer 7, and it may use 2 or more types together by arbitrary combinations and a ratio.

There is no restriction | limiting in the formation method of the electron carrying layer 7. Therefore, it can form by the wet film-forming method, the vapor deposition method, or another method.

The film thickness of the electron transport layer 7 is arbitrary as long as the effect of this invention is not impaired remarkably. The film thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and on the other hand, usually 300 nm or less, preferably 100 nm or less.

[Electron injection layer]

The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the light emitting layer 5. In order to perform electron injection efficiently, it is preferable that the material which forms the electron injection layer 8 is a metal with low work function. Examples include alkali metals such as sodium and cesium and alkaline earth metals such as barium and calcium. As for the film thickness of the electron injection layer 8, 0.1 nm or more and 5 nm or less are preferable normally.

The electron injection layer 8 is a sodium, potassium, cesium, lithium, rubidium to an organic electron transport compound represented by metal complexes such as nitrogen-containing heterocyclic compounds such as vasophenanthroline and aluminum complexes of 8-hydroxyquinoline. By doping alkali metals such as Japanese Patent Application Laid-Open No. 10-270171, Japanese Patent Application Laid-Open No. 2002-100478, Japanese Patent Application Laid-Open No. 2002-100482, etc., the electron injection and transporting properties are improved to achieve excellent film quality. It is preferable because it becomes possible to make it possible. In this case, the film thickness is usually 5 nm or more, particularly preferably 10 nm or more, and usually 200 nm or less, particularly preferably 100 nm or less.

In addition, only 1 type may be used for the material of the electron injection layer 8, and 2 or more types may be used together by arbitrary combinations and a ratio.

There is no limitation on the method of forming the electron injection layer 8. Therefore, it can form by the wet film-forming method, the vapor deposition method, or another method.

[cathode]

The cathode 9 serves to inject electrons into a layer (electron injection layer 8 or light emitting layer 5, etc.) on the light emitting layer 5 side.

As the material of the cathode 9, it is possible to use a material used for the anode 2. As a material of the cathode 9, a metal having a low work function is preferable for efficiently injecting electrons. Specifically, suitable metals, such as tin, magnesium, indium, calcium, aluminum, silver, are mentioned, for example. Moreover, these alloys etc. are also used preferably. As a specific example, low work function alloy electrodes, such as a magnesium silver alloy, a magnesium indium alloy, and an aluminum lithium lithium alloy, are mentioned.

In addition, only 1 type may be used for the material of the negative electrode 9, and 2 or more types may be used together by arbitrary combinations and a ratio.

The film thickness of the negative electrode 9 is usually the same as that of the positive electrode 2.

In addition, for the purpose of protecting the negative electrode 9 made of a low work function metal, it is preferable to further laminate a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased. For this purpose, for example, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used. In addition, these materials may be used only by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

[Other layers]

The organic electroluminescent element which concerns on this invention may have another structure in the range which does not deviate from the meaning. For example, the organic electroluminescent device according to the present invention may have any layer other than the layer in the above description between the anode 2 and the cathode 9 so long as the performance thereof is not impaired. Any of the layers in the description may be omitted.

As a layer which you may have other than the layer in the said description, an electron blocking layer is mentioned, for example.

The electron blocking layer is usually formed between the hole injection layer 3 or the hole transport layer 4 and the light emitting layer 5. In the electron blocking layer, electrons moving from the light emitting layer 5 are prevented from reaching the hole injection layer 3, thereby increasing the probability of recombination of holes and electrons in the light emitting layer 5 and generating the excitons in the light emitting layer 5 There is a role of confining the inside and transporting holes injected from the hole injection layer 3 toward the light emitting layer 5 efficiently. In particular, when a phosphorescent material is used as a light emitting material or a blue light emitting material is used, it is effective to form an electron blocking layer.

Examples of the characteristics required for the electron blocking layer include high hole transport properties, large energy gaps (differences between HOMO and LUMO), and high excitation triplet levels (T1). In the present invention, when the light emitting layer 5 is produced by the wet film forming method as the organic layer according to the present invention, suitability of wet film forming is also required for the electron blocking layer. As a material used for such an electron blocking layer, the copolymer of dioctyl fluorene and triphenylamine represented by F8-TFB (international publication 2004/084260) etc. are mentioned.

In addition, only 1 type may be used for the material of an electron blocking layer, and it may use 2 or more types together by arbitrary combinations and a ratio.

There is no restriction | limiting in the formation method of an electron blocking layer. Therefore, it can form by the wet film-forming method, the vapor deposition method, or another method.

Moreover, lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II), for example, at the interface between the cathode 9 and the light emitting layer 5 or the electron transport layer 7. Inserting an ultrathin insulating film (0.1-5 nm) formed of (CsCO ₃ ) or the like is also an effective method for improving the efficiency of the device (Applied Physics Letters, 1997, Vol. 70, pp. 152; 10-74586; IEEE Transactions on Electron Devices, 1997, Vol. 44, pp. 1245; see SID 04 Digest, pp. 154, etc.).

Moreover, in the layer structure demonstrated above, components other than a board | substrate can also be laminated | stacked in reverse order. For example, if it is the laminated constitution of FIG. 1, the other component is carried out on the board | substrate 1 with the cathode 9, the electron injection layer 8, the electron carrying layer 7, the hole blocking layer 6, and the light emitting layer 5. , The hole transport layer 4, the hole injection layer 3, and the anode 2 may be formed in this order.

Moreover, the organic electroluminescent element which concerns on this invention can also be comprised by laminating | stacking components other than a board | substrate between two board | substrates which at least one has transparency.

Moreover, it is also possible to set it as the structure (structure which laminated two or more light emitting units) which laminated | stacked several components (light emitting units) other than a board | substrate. In that case, instead of the interfacial layer (between the light emitting units) (the two layers in the case where the anode is ITO and the cathode is Al), for example, a charge is formed of vanadium pentoxide (V ₂ O ₅ ) or the like. When a layer (Carrier Generation Layer: CGL) is formed, the barrier between stages is small, which is more preferable from the viewpoint of luminous efficiency and driving voltage.

In addition, the organic electroluminescent element which concerns on this invention may be comprised as a single organic electroluminescent element, and may be applied to the structure in which several organic electroluminescent element was arrange | positioned in the array form, and an anode and a cathode are arrange | positioned in XY matrix form. It may be applied to a configured configuration.

Moreover, each layer mentioned above may contain components other than what was demonstrated as a material, unless the effect of this invention is remarkably impaired.

[3] organic EL displays

The organic electroluminescence display of this invention is a display apparatus using the organic electroluminescent element of this invention mentioned above. There is no restriction | limiting in particular about the form and structure of the organic electroluminescence display of this invention. The organic electroluminescence display of this invention can be comprised in accordance with a conventional method using the organic electroluminescent element of this invention. Specifically, for example, the organic EL display device of the present invention is described in the method described in "Organic EL Display" (Omsa, August 20, 2004 issuance, Tokitou Shizuo, Adachi Chihaya, Murata Hideyuki). Can be formed.

[4] organic electroluminescent lighting

The organic EL illumination of this invention is illumination using the organic electroluminescent element of this invention mentioned above. The organic EL illumination of this invention does not have a restriction | limiting in particular about the form and structure of the organic EL illumination of this invention. The organic EL illumination of this invention can be comprised in accordance with a conventional method using the organic electroluminescent element of this invention.

[5] apparatus for manufacturing organic electroluminescent device

EMBODIMENT OF THE INVENTION Below, the manufacturing apparatus of the organic electroluminescent element of this invention is demonstrated with reference to drawings.

FIG. 2 is a diagram schematically showing an example of an internal structure of an apparatus for manufacturing an organic electroluminescent element of the present invention. FIG.

In FIG. 2, 11 is a housing | casing, and the wet-film-forming of an organic layer is performed in this housing 11. That is, a substrate for forming an organic layer in the housing 11 by a wet film formation method (for example, if the organic layer to be formed is a hole transporting layer, an anode and a hole injection layer are formed on the substrate, if necessary. If the organic layer to be used is a light emitting layer, an anode, and a hole transporting layer or a hole injection layer and a hole transporting layer formed as necessary) are charged on the substrate, and the coating film of the organic layer is formed by the above-mentioned wet film-forming method.

12 purifies the air supplied into this housing 11, reduces at least one or more of carbon dioxide concentration, sulfur oxide concentration, and nitrogen oxide concentration in the air, and the film forming environment 1 to 3 described above in the housing 11. Air purification means for forming a. In the air purifying means 12, for example, the above-described chemical filter, an activated carbon layer, an aqueous layer, or a combination thereof, which is formed by passing through air A introduced from the blower 13, is formed.

If it is a manufacturing apparatus of such an organic electroluminescent element, by supplying the purified air in the housing 11 by the simple apparatus mainly comprised by the blower 13, the air purification means 12, and the housing 11, Wet film-forming can be performed under the conditions of 1-3 film forming environments, and there is no problem of deterioration during film-forming, and the organic electroluminescent element of this invention which is high efficiency and long life can be manufactured efficiently with low cost equipment.

Example

Although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Measuring method of specific component in environment]

(1) Measurement method of carbon dioxide concentration

The carbon dioxide concentration in environment was measured by using "GC-2010" by Shimadzu Corporation. Specifically, a gas chromatograph was measured in Shimazu Corporation "GC-2010" by introducing the gas which mixed He standard gas and nitrogen gas containing carbon dioxide of predetermined density | concentration in various flow volume ratios. A calibration curve of carbon dioxide concentration and signal intensity of GC / TCD was prepared. Next, a predetermined amount of gas to be measured was collected in a syringe having a cock at the tip, and this was introduced into Shimadzu Corporation's "GC-2010" to carry out GC / TCD measurement. The carbon dioxide concentration was computed using the analytical curve mentioned above. In addition, the detection limit of carbon dioxide concentration was 0.04 g / m <3>.

(2) Measurement method of sulfur oxide concentration and nitrogen oxide concentration

The sulfur oxide concentration and nitrogen oxide concentration in the environment were measured by collecting the measurement target gas in water at 1.5 L / min for 1 hour, and analyzing this by an ion chromatograph analyzer "DX500 type" (manufactured by DIONEX). In addition, the detection limits of sulfur oxide concentration and nitrogen oxide concentration were both 0.1 µg / m 3.

(3) How to measure absolute humidity

Absolute humidity of the atmospheric atmosphere was measured using the testo "testo608-H2". In addition, the absolute humidity of nitrogen atmosphere was measured using "Model DS1000" by Alpha Moisture System.

Example 1

The organic electroluminescent element which has a structure shown in FIG. 1 was produced with the following method.

<Formation of Hole Injection Layer for ITO Substrate>

As the ITO substrate, an indium tin oxide (ITO) transparent conductive film having a film thickness of 150 nm was used as the anode 2 on the glass substrate 1.

Next, the high molecular compound HI-1 and 4-isopropyl-4'-methyldiphenyl iodonium tetrakis (pentafluorophenyl) borate which have a repeating structure shown below were mixed at the weight ratio 100 to 20. This mixture was dissolved in ethyl benzoate so that the total concentration was 2.0% by weight to prepare a composition. This composition was spin-coated on the said ITO board | substrate in two steps of 2 second at the spinner speed 500 rpm and 30 second at 1500 rpm in air | atmosphere. Then, the hole injection layer 3 with a film thickness of 30 nm was formed by heating at 230 degreeC for 1 hour.

[Formula 29]

<Formation of Hole Transport Layer>

Next, the composition which melt | dissolved the high molecular compound HT-1 which has a repeating structure shown below in cyclohexyl benzene so that it may become 1.0 weight% was prepared. This composition was spin-coated on the said hole injection layer 3 in 2 steps of the spinner rotation speed 500 rpm 2 second and 1500 rpm 120 second in dry nitrogen atmosphere. Then, the hole transport layer 4 with a film thickness of 15 nm was formed by heating at 230 degreeC for 1 hour.

[Formula 30]

<Formation of the light emitting layer>

Next, the blue fluorescent material BH-1 and BD-1 shown below were mixed at a weight ratio of 100 to 7. This mixture was dissolved in cyclohexylbenzene so that the total concentration was 6.0% by weight to prepare a composition. This composition was spin-coated on the said hole transport layer 4 in 2 steps of 2 second by the spinner rotation speed 500 rpm, and 120 second by 2250 rpm. In addition, spin coating was performed in the atmospheric atmosphere (The oxygen concentration is 21 volume% (it describes as "%" hereafter), and the absolute humidity is 7.2 g / kg (DA)) whose carbon dioxide concentration is 0.3 g / m <3>. Then, the light emitting layer 5 with a film thickness of 50 nm was formed by heating at 130 degreeC for 1 hour.

[Formula 31]

<Formation of Hole Blocking Layer and Electron Transport Layer>

Subsequently, the compound HB-1 shown below was deposited on the light emitting layer 5 by the vacuum evaporation method so that it might become 10 nm in film thickness, and the hole-blocking layer 6 was formed.

[Formula 32]

Further, tris (8-hydroxyquinolinato) aluminum was deposited on the hole blocking layer 6 by a vacuum evaporation method so as to have a film thickness of 20 nm, thereby forming an electron transport layer 7.

<Formation of Electron Injection Layer and Cathode>

Subsequently, lithium fluoride (LiF) was deposited on the electron transport layer 7 by a vacuum deposition method so as to have a thickness of 0.5 nm, thereby forming an electron injection layer 8. Thereafter, aluminum was deposited by a vacuum deposition method so as to have a film thickness of 80 nm, thereby forming a cathode 9.

<Bag>

Then, photocurable resin was apply | coated to the outer peripheral part of a glass plate in the nitrogen glove box, and the moisture getter sheet was provided in the center part of the glass plate. The element formed to the said glass plate and the cathode 9 was bonded together, ultraviolet light was irradiated only to the area | region to which photocurable resin was apply | coated, and the resin was hardened. This obtained the organic electroluminescent element.

Comparative Example 1

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out in a dry nitrogen atmosphere where the carbon dioxide concentration was below the detection limit (oxygen concentration was 1 ppm or less and absolute humidity was 0.0001 g / kg (DA) or less). In the same manner, the device was fabricated.

Comparative Example 2

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out under an atmospheric atmosphere (21 vol% oxygen concentration, 10.3 g / kg (DA) oxygen concentration) having a carbon dioxide concentration of 1.2 g / m 3. In the same manner, the device was fabricated.

[evaluation]

About the organic electroluminescent element of Example 1 and Comparative Examples 1 and 2 produced as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 1 as a relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the comparative example 1 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Formation environment of emitting layer evaluation atmosphere Oxygen concentration Absolute humidity
[g / kg (DA)] Carbon Dioxide Concentration [g / ㎥] Luminous efficiency Luminance Half Life Example 1 Waiting 21 volume% 7.2 0.3 1.06 1.04 Comparative Example 1 nitrogen 1 ppm or less 0.0001 or less Below detection limit 1.00 1.00 Comparative Example 2 Waiting 21 volume% 10.3 1.2 0.90 0.46

From Table 1, by reducing the carbon dioxide concentration in the film-forming environment of the light emitting layer, the organic electroluminescent device having the same performance as the organic electroluminescent device in which the light emitting layer was formed under an inert gas atmosphere even in an air atmosphere in which oxygen concentration and humidity were not controlled. I could see that I could get it.

Example 2

Example 1 except that the spin coat at the time of film formation of the light emitting layer 5 was carried out under an atmospheric atmosphere (21 vol% oxygen concentration, 6.7 g / kg (DA) oxygen concentration) having a sulfur oxide concentration of 0.2 µg / m 3. In the same manner as in the device was manufactured.

Comparative Example 3

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out under a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0001 g / kg (DA) or less) in which the sulfur oxide concentration was below the detection limit. In the same manner as in the device was manufactured.

[Comparative Example 4]

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out under an atmospheric atmosphere (21 vol% oxygen concentration, 9.4 g / kg (DA) oxygen concentration) having a sulfur oxide concentration of 4.2 µg / m 3. In the same manner as in the device was manufactured.

[evaluation]

About the organic electroluminescent element of Example 2 and Comparative Examples 3 and 4 produced as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 2 as a relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the comparative example 3 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Formation environment of emitting layer evaluation atmosphere Oxygen concentration Absolute humidity
[g / kg (DA)] Sulfur oxide concentration
[Μg / ㎥] Luminous efficiency Luminance Half Life Example 2 Waiting 21 volume% 6.7 0.2 1.00 1.05 Comparative Example 3 nitrogen 1 ppm or less 0.0001 or less Below detection limit 1.00 1.00 Comparative Example 4 Waiting 21 volume% 9.4 4.2 0.87 0.56

From Table 2, by reducing the sulfur oxide concentration in the film-forming environment of the light emitting layer, even in an atmospheric atmosphere in which oxygen concentration and humidity are not controlled, an organic electroluminescence having the same performance as the organic electroluminescent element in which the light emitting layer was formed in an inert gas atmosphere. It was found that the device can be obtained.

Example 3

The spin coat at the time of film formation of the light emitting layer 5 was the same as in Example 1 except that the nitrogen oxide concentration was below the detection limit (at an oxygen concentration of 21 vol% and absolute humidity of 5.6 g / kg (DA)). The device was manufactured.

[Comparative Example 5]

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out in a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0001 g / kg (DA) or less) in which the nitrogen oxide concentration was below the detection limit. In the same manner as in the device was manufactured.

Comparative Example 6

Example 1 except that the spin coat during the film formation of the light emitting layer 5 was carried out under an atmospheric atmosphere (oxygen concentration 21 vol%, absolute humidity 7.6 g / kg (DA)) having a nitrogen oxide concentration of 4.3 µg / m 3. In the same manner as in the device was manufactured.

[evaluation]

About the organic electroluminescent elements of Example 3 and Comparative Examples 5 and 6 produced as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 3 as a relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the comparative example 5 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Formation environment of emitting layer evaluation atmosphere Oxygen concentration Absolute humidity
[g / kg (DA)] Nitrogen oxide concentration
[Μg / ㎥] Luminous efficiency Luminance Half Life Example 3 Waiting 21 volume% 5.6 Below detection limit 0.96 0.99 Comparative Example 5 nitrogen 1 ppm or less 0.0001 or less Below detection limit 1.00 1.00 Comparative Example 6 Waiting 21 volume% 7.6 4.3 0.82 0.36

From Table 3, by reducing the concentration of nitrogen oxides in the film-forming environment of the light emitting layer, even in an atmospheric atmosphere in which oxygen concentration and humidity are not controlled, organic electroluminescence having the same performance as the organic electroluminescent element in which the light emitting layer was formed in an inert gas atmosphere. It was found that the device can be obtained.

Example 4

An element was manufactured in the same manner as in Example 1 except that the method of forming the light emitting layer 5 was changed as follows.

The blue fluorescent light emitting material BH-1 used in Example 1 and the following GH-1 and GD-1 which are green phosphorescent light emitting materials were mixed at a weight ratio of 25 to 75 to 10. The composition which melt | dissolved this mixture in cyclohexylbenzene so that the total concentration might be 5.0 weight% was prepared. The composition was spin-coated on the hole transport layer 4 in two stages of spinner rotational speed 500 rpm for 2 seconds and 2000 rpm for 120 seconds. In addition, the spin coat has an atmosphere of carbon dioxide concentration, sulfur oxide concentration, and nitrogen oxide concentration of 0.3 g / m 3, 0.2 µg / m 3, and 1.9 µg / m 3, respectively (oxygen concentration of 21% by volume and absolute humidity of 13.9 g / kg). (DA)). Then, the light emitting layer 5 with a film thickness of 50 nm was formed by heating at 130 degreeC for 1 hour.

[Formula 33]

Comparative Example 7

The spin coat at the time of film formation of the light emitting layer 5 has a dry nitrogen atmosphere in which carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration are all below the detection limit (oxygen concentration is 1 ppm or less, absolute humidity is 0.0001 g / kg (DA) or less). Except having performed below, it carried out similarly to Example 4, and produced the element.

[evaluation]

About the organic electroluminescent elements of Example 4 and Comparative Example 7 produced as described above, the respective luminous efficiency and luminance half life were measured. The result was shown in Table 4 as a relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the comparative example 7 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Formation environment of emitting layer evaluation atmosphere Oxygen concentration Absolute Humidity [g / ㎏ (DA)] Carbon dioxide concentration [g / ㎥] Sulfur oxide concentration [㎍ / ㎥] Nitrogen oxide concentration [㎍ / ㎥] Luminous efficiency Luminance Half Life Example 4 Waiting 21 volume% 13.9 0.3 0.2 1.9 1.02 1.03 Comparative Example 7 nitrogen 1 ppm or less 0.0001 or less Below detection limit Below detection limit Below detection limit 1.00 1.00

From Table 4, even in the organic electroluminescent element using the green phosphorescent light emitting material as the light emitting material of the light emitting layer, the oxygen concentration and the humidity are not controlled by reducing the carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration in the film forming environment of the light emitting layer. It was found that even in the air atmosphere, an organic electroluminescent device having a performance equivalent to that of the organic electroluminescent device in which the light emitting layer was formed in an inert gas atmosphere can be obtained.

Reference Example 1

An element was produced in the same manner as in Example 1 except that the method of forming the light emitting layer 5 was changed as follows.

The blue fluorescent material BH-1 and BD-1 used in Example 1 were mixed at a weight ratio of 100 to 7. The composition which melt | dissolved this mixture in cyclohexylbenzene so that the total concentration might be 3.8 weight% was prepared. The composition was spin-coated on the hole transport layer 4 in two stages of spinner rotational speed 500 rpm for 2 seconds and 1500 rpm for 120 seconds under a dry nitrogen atmosphere. Then, the light emitting layer 5 with a film thickness of 50 nm was formed by drying similarly to Example 1. Then, the element formed to this light emitting layer 5 was made into the atmospheric atmosphere (The oxygen concentration is 21 volume%) whose carbon dioxide concentration, nitrogen oxide concentration, and sulfur oxide concentration are 0.3 g / m <3>, 1.9 microgram / m <3>, and 0.2 microgram / m <3>, respectively. And absolute humidity at 7.6 g / kg (DA)) for 30 minutes. Thereafter, the hole blocking layer, the electron transport layer, the electron injection layer, and the cathode were formed and sealed in the same manner as in Example 1.

Reference Example 2

An element formed up to the light emitting layer 5 was provided with an atmospheric atmosphere having a carbon dioxide concentration, a nitrogen oxide concentration, and a sulfur oxide concentration of 0.7 g / m 3, 3.1 μg / m 3 and 2.2 μg / m 3, respectively (oxygen concentration of 21% by volume and absolute humidity). Production was carried out in the same manner as in Reference Example 1 except that the mixture was stored under 7.5 g / kg (DA) for 30 minutes.

In addition, this storage environment is the atmosphere where carbon dioxide concentration, nitrogen oxide concentration, and sulfur oxide concentration which were used by the reference example 1 are 0.3 g / m <3>, 1.9 microgram / m <3>, 0.2 microgram / m <3>, respectively, carbon dioxide concentration, nitrogen oxide concentration, and sulfur. It was formed by mixing common atmospheres with oxide concentrations of 1.2 g / m 3, 4.3 μg / m 3 and 4.2 μg / m 3, respectively, in the same volume ratio.

Reference Example 3

The device formed up to the light emitting layer 5 was formed under a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0001 g / kg (DA) or less) in which carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration were all below the detection limit. Except having stored for a minute, the element was produced like reference example 1

Reference Example 4

An element formed up to the light emitting layer 5 was provided with an atmospheric atmosphere having a carbon dioxide concentration, a nitrogen oxide concentration, and a sulfur oxide concentration of 1.2 g / m 3, 4.3 μg / m 3 and 4.2 μg / m 3, respectively (oxygen concentration of 21% by volume and absolute humidity). A device was fabricated in the same manner as in Reference Example 1 except that the reaction product was stored under 7.6 g / kg (DA) for 30 minutes.

[evaluation]

About the organic electroluminescent elements of Reference Examples 1-4 manufactured as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 5 as a relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of Reference Example 3 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Storage environment of light emitting layer evaluation atmosphere Oxygen concentration Absolute Humidity [g / ㎏ (DA)] Carbon dioxide concentration [g / ㎥] Sulfur oxide concentration [㎍ / ㎥] Nitrogen oxide concentration [㎍ / ㎥] Luminous efficiency Luminance Half Life Reference Example 1 Waiting 21 volume% 7.6 0.3 0.2 1.9 0.96 1.11 Reference Example 2 Waiting 21 volume% 7.5 0.7 2.2 3.1 0.98 0.95 Reference Example 3 nitrogen 1 ppm or less 0.0001 or less Below detection limit Below detection limit Below detection limit 1.00 1.00 Reference Example 4 Waiting 21 volume% 7.6 1.2 4.2 4.3 0.85 0.50

As shown in Table 5, the atmosphere which reduced carbon dioxide concentration, nitrogen oxide concentration, and sulfur oxide concentration to 0.7 g / m <3> or less, 3.1 microgram / m <3> or less, and 2.2 microgram / m <3> or less in the storage environment after forming a light emitting layer, respectively It was found that the organic electroluminescent device stored in the atmosphere showed equivalent performance as compared with the organic electroluminescent device stored in the inert gas atmosphere.

Example 5

 Spin coating during film formation of the light emitting layer 5 was carried out under a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0016 g / kg (DA)) in which carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration were all below the detection limit. It carried out and manufactured the element similarly to Example 4 except having changed the formation method of the hole transport layer 4 as follows.

The composition which melt | dissolved in high molecular compound HT-1 in cyclohexyl benzene so that it might become 1.0 weight% was prepared. The composition was prepared in an atmosphere of carbon dioxide concentration, sulfur oxide concentration, and nitrogen oxide concentration of 0.3 g / m 3, 0.2 µg / m 3 and 1.9 µg / m 3, respectively (oxygen concentration of 21% by volume and absolute humidity of 13.1 g / kg (DA )), Onto the hole injection layer 3 was spin-coated in two stages of spinner rotational speed 500 rpm for 2 seconds and 1500 rpm for 120 seconds. Then, the hole transport layer 4 with a film thickness of 15 nm was formed by heating at 230 degreeC for 1 hour.

Comparative Example 8

Spin coating during the film formation of the hole transport layer 4 is carried out in a dry nitrogen atmosphere where the carbon dioxide concentration, sulfur oxide concentration and nitrogen oxide concentration are all below the detection limit (oxygen concentration is 1 ppm or less and absolute humidity is 0.0001 g / kg (DA) or less). The device was fabricated in the same manner as in Example 5 except that the device was carried out in the above).

[evaluation]

About the organic electroluminescent elements of Example 5 and Comparative Example 8 produced as described above, the respective luminous efficiency and luminance half life were measured. The result was shown in Table 6 by the relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the comparative example 8 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Film deposition environment of hole transport layer evaluation atmosphere Oxygen concentration Absolute Humidity [g / ㎏ (DA)] Carbon dioxide concentration [g / ㎥] Sulfur oxide concentration [㎍ / ㎥] Nitrogen oxide concentration [㎍ / ㎥] Luminous efficiency Luminance Half Life Example 5 Waiting 21 volume% 13.1 0.3 0.2 1.9 0.99 0.99 Comparative Example 8 nitrogen 1 ppm or less 0.0001 or less Below detection limit Below detection limit Below detection limit 1.00 1.00

From Table 6, by reducing the carbon dioxide concentration, the sulfur oxide concentration, and the nitrogen oxide concentration in the film formation environment of the hole transport layer, the organic film in which the hole transport layer was formed under an inert gas atmosphere even in an air atmosphere in which oxygen concentration and humidity were not controlled. It turned out that the organic electroluminescent element which has the performance equivalent to an electroluminescent element can be obtained.

Reference Example 5

The device formed up to the light emitting layer 5 was stored for 15 minutes in a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0001 g / kg (DA) or less) in which the sulfur oxide concentration and the nitrogen oxide concentration were below the detection limit. A device was produced in the same manner as in Reference Example 1 except for the above.

Reference Example 6

An element formed up to the light emitting layer 5 was dried in a dry nitrogen atmosphere in which sulfur oxide and nitrogen oxide were added (sulfur oxide concentration of 0.1 vol% or more, nitrogen oxide concentration of 0.1 vol% or more, oxygen concentration of 1 ppm or less, absolute humidity A device was fabricated in the same manner as in Reference Example 1 except that the mixture was stored for 15 minutes under 0.0001 g / kg (DA) or less).

Reference Example 7

The device formed up to the light emitting layer 5 was placed under a nitrogen atmosphere (sulfur oxide concentration of 0.1 vol% or more, nitrogen oxide concentration of 0.1 vol% or more and oxygen concentration of 21 vol%) in which sulfur oxide, nitrogen oxide and oxygen were added. Except having stored for a minute, it carried out similarly to the reference example 1, and produced the element.

[evaluation]

About the organic electroluminescent elements of the reference examples 5-7 produced as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 7 by the relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the reference example 5 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner). In addition, about the reference example 7, the characteristic of the organic electroluminescent element deteriorated so that evaluation for evaluation could not be carried out.

Storage environment of light emitting layer evaluation atmosphere Oxygen concentration Sulfur oxide concentration Nitrogen oxide concentration Luminous efficiency Luminance Half Life Reference Example 5 nitrogen 1 ppm or less Below detection limit Below detection limit 1.00 1.00 Reference Example 6 nitrogen 1 ppm or less 0.1 volume% or more 0.1 volume% or more 0.98 1.00 Reference Example 7 Waiting 21 volume% 0.1 volume% or more 0.1 volume% or more Not rated Not rated

As shown in Table 7, the organic electroluminescent element stored in the atmosphere where nitrogen oxide concentration and sulfur oxide concentration are 0.1 volume% or more and oxygen concentration of 1 ppm or less with respect to the storage environment after forming a light emitting layer is an inert gas atmosphere, respectively. Compared with the organic electroluminescent element stored below, it turned out that it shows the equivalent performance. In contrast, with respect to the storage environment after forming the light emitting layer, the organic electroluminescent device stored in an atmosphere having a nitrogen oxide concentration and a sulfur oxide concentration of 0.1 vol% or more and an oxygen concentration of 21 vol%, respectively, was stored under an inert gas atmosphere. Compared with the organic electroluminescent element, it turned out that a characteristic falls remarkably.

Reference Example 8

Reference Example 1 except that the device formed up to the light emitting layer 5 was stored for 15 minutes under a dry nitrogen atmosphere (with an oxygen concentration of 1 ppm or less and an absolute humidity of 0.0001 g / kg (DA) or less) in which the carbon dioxide concentration was below the detection limit. In the same manner as in the device was manufactured.

Reference Example 9

The device was fabricated in the same manner as in Reference Example 1 except that the device formed up to the light emitting layer 5 was stored for 15 minutes under a mixed atmosphere of carbon dioxide and nitrogen (carbon dioxide concentration of 80 vol% or more and oxygen concentration of 1 ppm or less). It was.

Reference Example 10

The device formed up to the light emitting layer 5 was stored in the same manner as in Reference Example 1 except that the device was stored for 15 minutes under a mixed atmosphere of carbon dioxide, nitrogen, and oxygen (carbon dioxide concentration of 80% by volume or more, oxygen concentration of 5% by volume). Was produced.

[evaluation]

About the organic electroluminescent elements of the reference examples 8-10 produced as mentioned above, each luminous efficiency and luminance half life were measured. The result was shown in Table 8 by the relative value which set the luminous efficiency and luminance half life of the organic electroluminescent element of the reference example 8 to 1.00, respectively. The luminance half life is the time required from the initial luminance to half the luminance of the initial luminance. In this case, the initial luminance was set to 1000 cd / m 2 (the following evaluations were all performed in the same manner).

Storage environment of light emitting layer result atmosphere Oxygen concentration Carbon dioxide concentration
Luminous efficiency Luminance Half Life Reference Example 8 nitrogen 1 ppm or less Below detection limit
1.00 1.00 Reference Example 9 nitrogen 1 ppm or less 80% by volume or more
0.96 1.00 Reference Example 10 Waiting 5% by volume 80% by volume or more
0.96 0.85

As shown in Table 8, with respect to the storage environment after forming the light emitting layer, the organic electroluminescent element stored in an atmosphere having a carbon dioxide concentration of 80% by volume and an oxygen concentration of 1 ppm or less was stored in an inert gas atmosphere. Compared with the element, it was found to exhibit equivalent performance. In contrast, with respect to the storage environment after forming the light emitting layer, the organic electroluminescent device stored in an atmosphere having a carbon dioxide concentration of 80% by volume or more and an oxygen concentration of 5% by volume is compared with an organic electroluminescent device stored in an inert gas atmosphere. It turned out that the characteristic falls.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on the JP Patent application (Japanese Patent Application No. 2010-057606) of an application on March 15, 2010, The content is taken in here as a reference.

Industrial availability

The present invention relates to various fields in which organic electroluminescent devices are used, for example, flat panel displays (for example, for OA computers or wall-mounted TVs) or light sources utilizing characteristics as surface light emitters (for example, light sources for copiers, It can be used suitably in the field | areas, such as a liquid crystal display and the backlight light source of instrument instruments, a display panel, a cover, etc.

One … Board
2 … anode
3…. Hole injection layer
4 … Hole transport layer
5…. Light emitting layer
6. Hole blocking layer
7. Electron transport layer
8 … Electron injection layer
9. cathode
10... Organic electroluminescent element
11. housing
12... Air purification means
13. air blower
A… air

Claims (1)

An apparatus for producing an organic electroluminescent element having an organic layer between an anode and a cathode,
At least one layer contained in the organic layer is formed by a wet film formation method using an organic electroluminescent device composition containing an organic electroluminescent device material and a solvent while maintaining an oxygen concentration in the atmosphere at 18 to 22% by volume. Film forming means for forming, drying means for drying the formed film,
The manufacturing apparatus of the organic electroluminescent element which has air purification means which reduces the carbon dioxide concentration in the atmosphere of the said film-forming means, and also reduces any one or more of sulfur oxide concentration and nitrogen oxide concentration.

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